Recycling of EDTA solution after soil washing of Pb, Zn, Cd and As contaminated soil

Soil washing with EDTA is known to be an effective means of removing toxic metals from contaminated soil. A practical way of recycling of used soil washing solution remains, however, an unsolved technical problem. We demonstrate here, in a laboratory scale experiment, the feasibility of using acid precipitation to recover up to 50% of EDTA from used soil washing solution obtained after extraction of Pb (5330 mg kg⁻¹), Zn (3400 mg kg⁻¹), Cd (35 mg kg⁻¹) and As (279 mg kg⁻¹) contaminated soil. Up to 100% of EDTA residual in the washing solution and 100%, 97%, 98% and 100% of initial Pb, Zn, Cd and As concentration in the solution, respectively, were removed in an electrolytic cell using a graphite anode. We employed the recovered EDTA and treated washing solution to prepare recycled soil washing solution with the same potential for extracting toxic metals from soil as the original. The efficiency of soil washing depends on the EDTA concentration. Using twice recycled 30 mmol EDTA kg⁻¹ soil, we removed 44%, 20%, 53% and 61% of Pb, Zn, Cd and As, respectively, from contaminated soil.     

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

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

Estimation of daily intake of potentially toxic elements from urban street dust and the role of oral bioaccessibility testing

The pseudo-total and oral bioaccessible concentration of six potentially toxic elements (PTEs) in urban street dust was investigated. Typical pseudo-total concentrations across the sampling sites ranged from 4.4 to 8.6 mg kg⁻¹ for As, 0.2-3.6 mg kg⁻¹ for Cd, 25-217 mg kg⁻¹ for Cu, 14-46 mg kg⁻¹ for Ni, 70-4261 mg kg⁻¹ for Pb, and, 111-652 mg kg⁻¹ for Zn. This data compared favourably with other urban street dust samples collected and analysed in a variety of cities globally; the exception was the high level of Pb determined in a specific sample in this study. The oral bioaccessibility of PTEs in street dust is also assessed using in vitro gastrointestinal extraction (Unified Bioaccessibility Method, UBM). Based on a worst case scenario the oral bioaccessibility data estimated that Cd and Zn had the highest % bioaccessible fractions (median >45%) while the other PTEs i.e. As, Cu, Ni and Pb had lower % bioaccessible fractions (median <35%). The pseudo-total and bioaccessible concentrations of PTEs in the samples has been compared to estimated tolerable daily intake values based on unintentional soil/dust consumption. Cadmium, Cu and Ni are well within the oral tolerable daily intake rates. With respect to As and Pb, only the latter exceeds the TDI_oral if we model ingestion rate based on atmospheric ‘dustiness’ rather than the US EPA (2008) unintentional soil/dust consumption rate of 100 mg d⁻¹. We consider it unlikely that even a child with pica tendencies would ingest as much as 100 mg soil/dust during a daily visit to the city centre, and in particular to the sites with elevated Pb concentrations observed in this study.     

Effects of biochar and the earthworm Eisenia fetida on the bioavailability of polycyclic aromatic hydrocarbons and potentially toxic elements

Polycyclic aromatic hydrocarbons (PAHs) and potentially toxic elements (PTEs) were monitored over 56 days in calcareous contaminated-soil amended with either or both biochar and Eisenia fetida. Biochar reduced total (449 to 306 mg kg⁻¹) and bioavailable (cyclodextrin extractable) (276 to 182 mg kg⁻¹) PAHs, PAH concentrations in E. fetida (up to 45%) but also earthworm weight. Earthworms increased PAH bioavailability by >40%. Combined treatment results were similar to the biochar-only treatment. Earthworms increased water soluble Co (3.4 to 29.2 mg kg⁻¹), Cu (60.0 to 120.1 mg kg⁻¹) and Ni (31.7 to 83.0 mg kg⁻¹) but not As, Cd, Pb or Zn; biochar reduced water soluble Cu (60 to 37 mg kg⁻¹). Combined treatment results were similar to the biochar-only treatment but gave a greater reduction in As and Cd mobility. Biochar has contaminated land remediation potential, but its long-term impact on contaminants and soil biota needs to be assessed.     

Identification of Chinese cabbage genotypes with low cadmium accumulation for food safety

The pot-culture experiment and field studies were conducted to screen out and identify cadmium (Cd) excluders from 40 Chinese cabbage genotypes for food safety. The results of the pot-culture experiment indicated that the shoot Cd concentrations under three treatments (1.0, 2.5 and 5.0 mg Cd kg⁻¹ Soil) varied significantly (p < 0.05), with average values of 0.70, 3.07 and 5.83 mg kg⁻¹, respectively. The Cd concentrations in 12 cabbage genotypes were lower than 0.50 mg kg⁻¹. The enrichment factors (EFs) and translocation factors (TFs) in 8 cabbage genotypes were lower than 1.0. The field studies further identified Lvxing 70 as a Cd-excluder genotype (CEG), which is suitable to be planted in low Cd-contaminated soils (Cd concentration should be lower than 1.25 mg kg⁻¹) for food safety.     

Mercury accumulation in the surface layers of mountain soils: a case study from the Karkonosze Mountains, Poland

The study was aimed to examine total concentrations and pools of Hg in surface layers of soils in the Karkonosze Mountains, dependent on soil properties and site locality. Soil samples were collected from a litter layer and the layers 0-10 cm and 10-20 cm, at 68 sites belonging to the net of a monitoring system, in two separate areas, and in three altitudinal zones: below 900 m, 900-1100 m, and over 1100 m. Air-borne pollution was the major source of mercury in soils. Hg has accumulated mainly in the litter (where its concentrations were the highest), and in the layer 0-10 cm. Hg concentrations in all samples were in the range 0.04-0.97 mg kg⁻¹, with mean values 0.38, 0.28, and 0.14 mg kg⁻¹ for litter and the layers 0-10 cm and 10-20 cm, respectively. The highest Hg concentrations in the litter layer were found in the intermediate altitudinal zone, whereas Hg concentrations in the layer 0-10 cm increased with increasing altitude. Soil quality standard for protected areas (0.50 mg kg⁻¹) was exceeded in a few sites. The pools of Hg accumulated in soils were in the range: 0.8-84.8 mg m⁻², with a mean value of 16.5 mg m⁻², and they correlated strongly with the pools of stored organic matter.     

Highly charged swelling mica reduces Cu bioavailability in Cu-contaminated soils

This is the first test of a highly charged swelling mica's (Na-2-mica) ability to reduce the plant-absorbed Cu in Cu-contaminated soils from Chile. Perennial ryegrass (Lolium perenne L.) was grown in two acid soils (Sector 2: pH 4.2, total Cu = 172 mg Cu kg⁻¹ and Sector 3: pH 4.2, total Cu = 112 mg Cu kg⁻¹) amended with 0.5% and 1% (w/w) mica, and 1% (w/w) montmorillonite. At 10 weeks of growth, both mica treatments decreased the shoot Cu of ryegrass grown in Sector 2 producing shoot Cu concentrations above 21-22 mg Cu kg⁻¹ (the phytotoxicity threshold for that species), yet the mica treatments did not reduce shoot Cu concentrations when grown in Sector 3, which were at a typical level. The mica treatments improved shoot growth in Sector 3 by reducing free and extractable Cu to low enough levels where other nutrients could compete for plant absorption and translocation. In addition, the mica treatments improved root growth in both soils, and the 1% mica treatment reduced root Cu in both soils. This swelling mica warrants further testing of its ability to assist re-vegetation and reduce Cu bioavailability in Cu-contaminated surface soils.     

Selenium fractions in organic matter from Se-rich soils and weathered stone coal in selenosis areas of China

A high degree of association between Selenium (Se) and organic matter has been demonstrated in natural environments, but Se fractions and speciation in organic matter is unclear. In this study, a method for quantifying organic matter associated with Se (OM-Se) was developed to investigate Se fractions in organic matter in Se-rich soils and weathered stone coal from Enshi, China, where Se poisoning of humans and livestock has been documented. Initially, Se was extracted using water and a phosphate buffer. Subsequently, OM-Se was extracted using NaOH, and then speciated into Se associated with fulvic acids (FA-Se) and humic acids (HA-Se). Both FA-Se and HA-Se were further speciated into the weakly bound and strongly bound fractions using a customized hydride generation reactor. The results show that FA-Se (1.91-479 mg kg⁻¹) is the predominant form of Se in all Se-rich soils and the weathered stone coal samples, accounting for more than 62% of OM-Se (3.07-484 mg kg⁻¹). Weakly bound FA-Se (1.33-450 mg kg⁻¹) was prevalent in the total FA-Se, while weakly bound HA-Se (0.62-26.2 mg kg⁻¹) was variable in the total HA-Se (1.15-32.5 mg kg⁻¹). These data indicate that OM-Se could play a significant source and sink role in the biogeochemical cycling of Se in the supergene environment. Weakly bound FA-Se seems to act as a potential source for bioavailable Se, whereas strongly bound HA-Se is a possible OM-Se sink which is not readily transformed into bioavailable Se.     

Amendment of arsenic and chromium polluted soil from wood preservation by iron residues from water treatment

An iron-rich water treatment residue (WTR) consisting mainly of ferrihydrite was used for immobilization of arsenic and chromium in a soil contaminated by wood preservatives. A leaching batch experiment was conducted using two soils, a highly contaminated soil (1033 mg kg⁻¹ As and 371 mg kg⁻¹ Cr) and slightly contaminated soil (225 mg kg⁻¹ As and 27 mg kg⁻¹ Cr). Compared to an untreated reference soil, amendment with 5% WTR reduced leaching in the highly contaminated soil by 91% for Cr and 98% for As. No aging effect was observed after 103 d. In a small field experiment, soil was mixed with 2.5% WTR in situ. Pore water was extracted during 3 years from the amended soil and a control site. Pore water arsenic concentrations in the amended soil were more than two orders of magnitude lower than in the control for the upper samplers. An increased release of arsenic was observed during winter in both fields, mostly in the deepest samplers. This is likely due to the formation of a pseudo-gley because of precipitation surplus. Stabilization of arsenic and chromium contaminated soil using WTR is a promising method but the transformation of ferrihydrite in soil proves a concern in case of waterlogged soils. Still the amendment minimized the leaching of arsenic, even in cases of seasonal releases.     

Organochlorine pesticide in fresh and pasteurized cow's milk from Kampala markets

Fresh and pasteurized milk samples from Kampala markets were analyzed for organochlorine pesticides using a gas chromatograph equipped with an electron capture detector. Five organochlorine pesticides, namely; aldrin, dieldrin, endosulfan, lindane, DDT and its metabolites were detected in the milk samples and confirmed with a gas chromatograph equipped with a mass spectrometer [GC-MS]. The mean values are expressed in mg kg⁻¹ milk fat (mf) basis. The mean concentration in the fresh milk (n = 54) were: 0.026 ± 0.003 mg kg⁻¹ mf; 0.002 ± 0.0003 mg kg⁻¹, below the detection limit; 0.007 ± 0.003 mg kg⁻¹, 0.009 ± 0.002 mg kg⁻¹ milk fat for lindane, endosulfan dieldrin and aldrin, respectively. The mean concentrations of p,p′-DDE; p,p′-DDT and o,p′-DDT were 0.009 ± 0.002 mg kg⁻¹; 0.033 ± 0.007 mg kg⁻¹ and 0.008 ± 0.001 mg kg⁻¹ mf, respectively in the fresh milk samples.In the pasteurized milk samples (n = 47), the mean concentrations recorded were: 0.008 ± 0.003 mg kg⁻¹, 0.025 ± 0.004 mg kg⁻¹, and 0.007 ± 0.001 mg kg⁻¹, respectively for p,p′-DDE; p,p′-DDT and o,p′-DDT.Alpha and beta-endosulfan recorded the concentration below the detection limit and the mean of 0.022 ± 0.001 mg kg⁻¹ mf, 0.005 ± 0.002 mg kg⁻¹ mf, and 0.006 ± 0.0002 mg kg⁻¹ mf, respectively for lindane, dieldrin and aldrin. Although, most of the residues detected were above the residue limits set by the FAO/WHO (2008), bioaccumulation of these residues is likely to pose health risks to the consumers of milk in Uganda.     

Effects of petroleum contamination on soil microbial numbers, metabolic activity and urease activity

The influence of petroleum contamination on soil microbial activities was investigated in 13 soil samples from sites around an injection water well (Iw-1, 2, 3, 4) (total petroleum hydrocarbons (TPH): 7.5-78 mg kg⁻¹), an oil production well (Op-1, 2, 3, 4, 5) (TPH: 149-1110 mg kg⁻¹), and an oil spill accident well (Os-1, 2, 3, 4) (TPH: 4500-34 600 mg kg⁻¹). The growth rate constant (μ) of glucose stimulated organisms, determined by microcalorimetry, was higher in Iw soil samples than in Op and Os samples. Total cultivable bacteria and fungi and urease activity also decreased with increasing concentration of TPH. Total heat produced demonstrated that TPH at concentrations less than about 1 g kg⁻¹ soil stimulated anaerobic respiration. A positive correlation between TPH and soil organic matter (OM) and stimulation of fungi-bacteria-urease at low TPH doses suggested that TPH is bound to soil OM and slowly metabolized in Iw soils during OM consumption. These methods can be used to evaluate the potential of polluted soils to carry out self-bioremediation by metabolizing TPH.     

Correlation of foliar MT2b expression with Cd and Zn concentrations in hybrid aspen (Populus tremula × tremuloides) grown in contaminated soil

Metal uptake and its effect on foliar metallothionein 2b (MT2b) mRNA levels were studied in hybrid aspen (Populus tremula × tremuloides) in field conditions. The trees were planted on a site contaminated with several metals, including cadmium (mean 5.1 mg kg⁻¹), chromium (80 mg kg⁻¹), copper (180 mg kg⁻¹), nickel (81 mg kg⁻¹), vanadium (240 mg kg⁻¹) and zinc (520 mg kg⁻¹). Of the ten trace elements analyzed, only Cd and Zn accumulated in the leaves with maximal foliar concentrations of 35 and 2400 mg kg⁻¹ (dry weight), respectively. There was a strong correlation between Cd and Zn concentrations and bioaccumulation factors (concentration in plant/soil) in the leaves, branches and roots, suggesting similar transport mechanisms for these two metals. The levels of MT2b correlated with Cd and Zn concentrations in the leaves, demonstrating that increased MT2b expression is one of the responses of hybrid aspen to chronic metal exposure.     

Influence of humified organic matter on copper behavior in acid polluted soils

The main purpose of this work was to identify the role of soil humic acids (HAs) in controlling the behavior of Cu(II) in vineyard soils by exploring the relationship between the chemical and binding properties of HA fractions and those of soil as a whole. The study was conducted on soils with a sandy loam texture, pH 4.3-5.0, a carbon content of 12.4-41.0 g kg⁻¹ and Cu concentrations from 11 to 666 mg kg⁻¹. The metal complexing capacity of HA extracts obtained from the soils ranged from 0.69 to 1.02 mol kg⁻¹, and the stability constants for the metal ion-HA complexes formed, log K, from 5.07 to 5.36. Organic matter-quality related characteristics had little influence on Cu adsorption in acid soils, especially if compared with pH, the degree of Cu saturation and the amount of soil organic matter.     

Organ-wise accumulation of fluoride in Prosopis juliflora and its potential for phytoremediation of fluoride contaminated soil

Fluoride (F) contamination is a global environmental problem, as there is no cure of fluorosis available yet. Prosopis juliflora is a leguminous perennial, phreatophyte tree, widely distributed in arid and semi-arid regions of world. It extensively grows in F endemic areas of Rajasthan (India) and has been known as a “green” solution to decontaminate cadmium, chromium and copper contaminated soils. This study aims to check the tolerance potential of P. juliflora to accumulate fluoride. For this work, P. juliflora seedlings were grown for 75 d on soilrite under five different concentrations of F viz., control, 25, 50, 75 and 100 mg NaF kg⁻¹. Organ-wise accumulation of F, bioaccumulation factor (BF), translocation factor (TF), growth ratio (GR) and F tolerance index (TI) were examined. Plant accumulated high amounts of F in roots. The organ-wise distribution showed an accumulation 4.41 mg kg⁻¹dw, 12.97 mg kg⁻¹dw and 16.75 mg kg⁻¹dw F, in stem, leaves and roots respectively. The results indicated significant translocation of F from root into aerial parts. The bioaccumulation and translocation factor values (>1.0) showed high accumulation efficiency and tolerance of P. juliflora to F. It is concluded that P. juliflora is a suitable candidate for phytoremediation purpose and can be explored further for the decontamination of F polluted soils.     

Distribution, source and risk assessment of polychlorinated biphenyls (PCBs) in urban soils of Beijing, China

The concentration of PCBs in urban soils of Beijing across six land types including business districts (BD), cultural and educational areas (CE), classical gardens (CG), public green (PG), residential areas (RA), and roadsides (RD) was investigated. The total concentrations of PCBs ranged from below method detection limit (M.D.L.) to 37.11 × 10⁻³ mg kg⁻¹ dry weight (mean: 11.70 × 10⁻³ mg kg⁻¹; median: 13.28 × 10⁻³ mg kg⁻¹), which was at a medium level compared with other cities around the world. In general, the levels of PCBs decreased from the center of Beijing city to the suburb, suggesting the increasing PCBs concentrations with the age of the urban area. For different types of land use, the highest level of PCBs was observed in CG soils which have the oldest age, and the homologue profiles were similar, which were predominated by lowly chlorinated congeners including di-, tri- and tetra-CBs. Principal component analysis indicated that local sources such as Aroclor 1016, 1242, and 1248 were important sources in addition to long-range transport of PCBs all over the world. Although the toxic equivalency (TEQ) concentrations of dioxin-like PCBs in all soil samples of Beijing were higher than those in other urban areas of China, they met the Canadian soil quality standard.     

Susceptibility of epigeic earthworm Eisenia fetida to agricultural application of six insecticides

Ecotoxicological risks of agricultural application of six insecticides to soil organisms were evaluated by acute toxicity tests under laboratory condition following OECD guidelines using the epigeic earthworm Eisenia fetida as the test organism. The organochlorine insecticide endosulfan (LC₅₀ - 0.002 mg kg⁻¹) and the carbamate insecticides aldicarb (LC₅₀ - 9.42 mg kg⁻¹) and carbaryl (LC₅₀ - 14.81 mg kg⁻¹) were found ecologically most dangerous because LC₅₀ values of these insecticides were lower than the respective recommended agricultural dose (RAD). Although E. fetida was found highly susceptible to the pyrethroid insecticide cypermethrin (LC₅₀ - 0.054 mg kg⁻¹), the value was higher than its RAD. The organophosphate insecticides chlorpyrifos (LC₅₀ - 28.58 mg kg⁻¹), and monocrotophos (LC₅₀ - 39.75 mg kg⁻¹) were found less toxic and ecologically safe because the LC₅₀ values were much higher than their respective RAD.     

Food utilization and growth of cutworm Spodoptera litura Fabricius larvae exposed to nickel,and its effect on reproductive potential

Food utilization and growth of the 5th and 6th instar Spodoptera litura Fabricius larvae, and its effect on reproduction potential was evaluated by feeding larvae diets with different doses of Ni for 3 generations. Dose-dependent relationships between Ni levels and food consumption and growth were variable with different larval developmental period and Ni exposure duration. RCR, AD and RGR of the 6th instar larvae were much more affected by Ni exposure than those of 5th instar larvae, and the effects were strongest in the 3rd generation. It was found that RCR was significantly stimulated after 1 and 20 mg kg⁻¹ Ni exposure, while AD was significantly inhibited after 1, 5, 10 and 40 mg kg⁻¹ Ni exposure. However, lower levels of Ni (?5 mg kg⁻¹) significantly increased and higher levels of Ni (?10 mg kg⁻¹) significantly decreased RGR. In 3 successive generations, 10 mg kg⁻¹ Ni significantly increased the ECI and ECD of the 5th instar larvae, and 5 mg kg⁻¹ Ni significantly increased the ECD of the 6th instar larvae. However, ECD were all significantly inhibited with 20 mg kg⁻¹ Ni exposure. Results also revealed that durations of larvae were shortened at low levels of Ni, but extended at high levels of Ni. Fecundity was inhibited by the highest Ni doses in each generation, while improved by low Ni doses in the 3rd generation. Hatching rates in all treatments were significantly decreased in a Ni dose-dependent manner. Study indicated that effects of Ni on these parameters were predominant with the increasing Ni exposure period.     

Probability of intellectual disability is associated with soil concentrations of arsenic and lead

Background

The association between metals in water and soil and adverse child neurologic outcomes has focused on the singular effect of lead (Pb), mercury (Hg), and arsenic (As). This study describes the complex association between soil concentrations of As combined with Pb and the probability of intellectual disability (ID) in children.

Methods

We used a retrospective cohort design with 3988 mother child pairs who were insured by Medicaid and lived during pregnancy and early childhood in South Carolina between 1/1/97 and 12/31/02. The children were followed until 6/1/08, using computerized service files, to identify the diagnosis of ID in medical records and verified by either school placement or disability service records. The soil was sampled using a uniform grid and analyzed for eight metals. The metal concentrations were interpolated using Bayesian Kriging to estimate concentration at individual residences.

Results

The probability of ID increased for increasing concentrations of As and Pb in the soil. The Odds Ratio for ID, for one unit change in As was 1.130 (95% confidence interval 1.048-1.218) for Pb was 1.002 (95% confidence interval 1.000-1.004). We identified effect modification for the infants based on their birth weight for gestational age status and only infants who were normal size for their gestational age had increased probability of ID based on the As and Pb soil concentrations (OR for As at normal weight for gestational age = 1.151 (95% CI: 1.061-1.249) and OR for Pb at normal for gestational age = 1.002 (95% CI: 1.002-1.004)). For normal weight for gestational age children when As = 22 mg kg⁻¹ and Pb = 200 mg kg⁻¹ the risk for ID was 11% and when As = 22 mg kg⁻¹and Pb = 400 mg kg⁻¹ the probability of ID was 65%.

Conclusion

The probability of ID is significantly associated with the interaction between Pb and As for normal weight for gestational age infants.     

Zinc accumulation and synthesis of ZnO nanoparticles using Physalis alkekengi L

A field survey and greenhouse experiments were conducted using Physalis alkekengi L. to investigate strategies of phytoremediation. In addition, ZnO nanoparticles were synthesized using P. alkekengi. P. alkekengi plants grew healthily at Zn levels from 50 to 5000 mg kg⁻¹ in soils. The plants incorporated Zn into their aerial parts (with mean dry weight values of 235-10,980 mg kg⁻¹) and accumulated biomass (with a mean dry weight of 25.7 g plant⁻¹) during 12 weeks. The synthesized ZnO nanoparticles showed a polydisperse behavior and had a mean size of 72.5 nm. The results indicate that P. alkekengi could be used for the remediation of zinc-contaminated soils. Moreover, the synthetic method of synthesizing ZnO nanoparticles from Zn hyperaccumulator plants constitutes a new insight into the recycling of metals in plant sources.