Sustainability of in situ remediation of Cu- and Cd-contaminated soils with one-time application of amendments in Guixi,China

Purpose

In situ immobilization of heavy metal-contaminated soils with the repeated incorporation of amendments can effectively reduce the bioavailability of soil heavy metals. However, the long-term application of amendments would lead to the destruction of soil structure and accumulation of soil toxic elements, ultimately affecting food security and quality. Thus, the sustainability of the amendments in a heavy metal-contaminated soil was evaluated from 2010 to 2012.

Materials and methods

Batch field experiments were conducted in the soils, which were amended with apatite (22.3 t ha^?1), lime (4.45 t ha^?1), and charcoal (66.8 t ha^?1), respectively. The amendments were applied only one time in 2009, and ryegrass was sown each year. Ryegrass and setaria glauca (a kind of weed) were harvested each year. Concentrations of copper (Cu) and cadmium (Cd) were determined by batch experiments. Five fractions of Cu and Cd were evaluated by a sequential extraction procedure.

Results and discussion

Ryegrass grew well in the amended soils in the first year, but it failed to grow in all the soils in the third year. However, setaria glauca could grow with higher biomass in all the amended soils. The treatment of apatite combined with plants was more effective than lime and charcoal treatments in removing Cu and Cd from the contaminated soils by taking biomass into account. Apatite had the best sustainable effect on alleviating soil acidification. The Cu and Cd concentrations of CaCl₂-extractable and exchangeable fractions decreased with the application of amendments. Moreover, apatite and lime could effectively maintain the bioavailability of Cu and Cd low.

Conclusions

Apatite had a better sustainable effect on the remediation of heavy metal-contaminated soils than lime and charcoal. Although all the amendment treated soils did not reduce soil total concentrations of Cu and Cd, they could effectively reduce the environmental risk of the contaminated soils. The findings could be effectively used for in situ remediation of heavy metal-contaminated soils.

     

Immobilization of Cu and Cd in a contaminated soil: one- and four-year field effects

Purpose

Many amendments have been applied to immobilize heavy metals in soil. However, little information is available on the changes of immobilization efficiencies of heavy metals in contaminated soils over time. This work investigated the immobilization efficiencies of copper (Cu) and cadmium (Cd) in contaminated soils in situ remediated with one-time application of three amendments for 1 year and 4 years.

Materials and methods

Apatite, lime, and charcoal were mixed with the topsoil of each plot with the amounts of 22.3, 4.45, and 66.8 t/ha, respectively. Soil chemical properties and fractions of Cu and Cd were examined after in situ remediation for 1 year and 4 years. Soil sorption and retention capacities and desorption proportions for Cu and Cd were investigated by batch experiments.

Results and discussion

The addition of amendments significantly increased soil pH, but decreased exchange acid and aluminum (Al). The amendments significantly decreased the CaCl₂ extractable Cu and Cd and transformed them from active to inactive fractions. After the application of amendments for 1 year, the maximum sorption capacities ranged from 35.6 to 38.8 mmol/kg for Cu and from 14.4 to 17.0 mmol/kg for Cd, which were markedly higher than those of the application of amendments for 4 years (Cu, 29.6–34.7 mmol/kg; Cd, 10.9–16.4 mmol/kg). Desorption proportions (D) of Cu and Cd using three extractants followed the order of \( {D}_{{\mathrm{NaNO}}_3}<{D}_{{\mathrm{CaCI}}_2}<{D}_{{\mathrm{MgCI}}_2} \) . Moreover, the retention capacities (R) of Cu and Cd both increased and followed the order of R _apatite?>?R _lime?>?R _charcoal, resulting in higher Cu and Cd in the amended soils than the untreated soil.

Conclusions

Apatite, lime, and charcoal increased the soil sorption and retention capacities of Cu and Cd and resulted in higher immobilization efficiencies in the amended soils than the untreated soil. However, the immobilization efficiencies of Cu and Cd decreased with the decrease of sorption capacities after 4 years. It was concluded that apatite had the best effect on the long-term stability of immobilized Cu and Cd and can be applied to immobilize heavy metals in contaminated soils.     

Simultaneous immobilization of lead,cadmium, and arsenic in combined contaminated soil with iron hydroxyl phosphate

Purpose

Combined contamination of lead (Pb), cadmium (Cd), and arsenic (As) in soils especially wastewater-irrigated soil causes environmental concern. The aim of this study is to develop a soil amendment for simultaneous immobilization of Pb, Cd, and As in combinative contaminated soil.

Materials and methods

A soil amendment of iron hydroxyl phosphate (FeHP) was prepared and characterized, and its potential application in simultaneous immobilization of Pb, Cd, and As in combined contaminated soil from wastewater-irrigated area was evaluated. The effects of FeHP dosage, reaction time, and soil moisture on Pb, Cd, and As immobilization in the soil were examined.

Results and discussion

The immobilization efficiencies of Pb, Cd, and As generally increased with the increasing of FeHP dosage. With FeHP dosage of 10 %, the immobilization percentages of NaHCO₃-extractable As and DTPA-extractable Pb and Cd reached 69, 59, and 44 %, respectively. The equilibrium time required for immobilization of these contaminants was in the following order: NaHCO₃-extractable As (0.25 days) < DTPA-extractable Cd(3 days) < DTPA-extractable Pb (7 days). However, the immobilization efficiencies of Pb, Cd, and As have not changed much under soil moisture varied from 20 to 100 %. According to the results of the sequential extraction, the percentages of Pb, Cd, and As in residual fractions increased after the application of FeHP amendment, while their percentages in exchangeable fractions decreased, illustrating that FeHP can effectively decrease the mobilities and bioavailabilities of Pb, Cd, and As in the soil. Moreover, the application of FeHP will not have soil acidification and soil structure problem based on the soil pH measurements and soil morphology.

Conclusions

FeHP can immobilize Pb, Cd, and As in the combinative contaminated soil from wastewater irrigation area simultaneously and effectively. Thus, it can be used as a potential soil amendment for the remediation of Pb, Cd, and As-combined contaminated soil.

     

The bioaccumulation of Cd in rice grains in paddy soils as affected and predicted by soil properties

Purpose

The area of cadmium (Cd)-contaminated soil in China is increasing due to the rapid development of the Chinese economy. To ensure that the rice produced in China meets current food safety and quality standards, the current soil quality standards for paddy soils urgently need to be updated.

Materials and methods

We conducted a pot experiment with 19 representative paddy soils from different parts of China to study the effects of soil properties on bioaccumulation of Cd in rice grains. The experiment included a control, a low treatment concentration (0.3 mg kg^–1 for pH?<?6.5 and 0.6 mg kg^–1 for pH?≥?6.5), and a high treatment concentration (0.6 mg kg^–1 for pH?<?6.5 and 1.2 mg kg^–1 for pH?≥?6.5) of Cd salt added to soils.

Results and discussion

The results showed that the Cd content in grains of the control and low and high Cd treatments ranged from 0.021 to 0.14, 0.07 to 0.27, and 0.12 to 0.33 mg kg^–1, respectively. Stepwise multiple regression analysis indicated that soil pH and organic carbon (OC) content could explain over 60 % of the variance in the (log-transformed) bioaccumulation coefficient (BCF) of Cd in grains across soils. Aggregated boosted trees analysis showed that soil pH and OC were the main factors controlling Cd bioavailability in paddy soils. Validation of the models against data from recent literature indicated that they were able to accurately predict the BCF in paddy soils.

Conclusions

These quantitative relationships between the BCF of Cd in grains and soil properties are helpful for developing soil-specific guidance on Cd safety threshold value for paddy soils.     

Metal removal from and microbial property improvement of a multiple heavy metals contaminated soil by phytoextraction with a cadmium hyperaccumulator Sedum alfredii H.

Purpose

Effects of phytoextraction by Sedum alfredii H., a native cadmium hyperaccumulator, on metal removal from and microbial property improvement of a multiple heavy metals contaminated soil were studied under greenhouse conditions.

Materials and methods

A rhizobox experiment with an ancient silver-mining ecotype of S. alfredii natively growing in Zhejiang Province, China, was conducted for remediation of a multiple heavy metals contaminated soil. The rhizobox was designed combining the root-shaking method for the separation of rhizospheric vs near-rhizospheric soils and prestratifying method for separation of sublayers rhizospheric soils (0–10 mm from the root) and bulk soil (>10 mm from the root). Soil and plant samplings were carried out after 3 and 6 months of plant growth.

Results and discussion

Cadmium (Cd), zinc (Zn), and lead (Pb) concentrations in shoots were 440.6, 11,893, and 91.2 mg kg^?1 after 6 months growth, and Cd, Zn, and Pb removed in the shoots were 0.862, 25.20, and 0.117 mg/plant. Microbial biomass C, basal respiration, urease, acid phosphatase, and invertase activities of the rhizospheric soils were significantly higher than that of unplanted soils after 6 months growth. Microbial biomass carbon (MBC) of 0–2 mm and basal respiration (BR) rate of 0–8 mm sublayer rhizospheric soils were significantly higher than that of bulk soil after 6 months growth. So were the three enzyme activities of 0–4 mm sublayer rhizospheric soils. BR rate and urease were significantly negatively correlated with soluble Cd, so were MBC, acid phosphatase, and intervase activities with soluble Zn, MBC, BR rate, and three enzyme activities with soluble Pb.

Conclusions

Harvesting shoots of S. alfredii could remove remarkable amounts of Cd, Zn, Pb, and lower water-soluble Cd, Zn, and Pb concentrations in the rhizospheric soils. MBC, BR rate, and enzyme activities of the metal polluted soil, especially the rhizospheric soils increased with phytoextraction process, which is attributed to the stimulation of soil microbes by planting as well as the decrease in soil-soluble metal concentration.     

Speciation of 90Sr and other metal cations in artificially contaminated soils: the influence of bone sorbent addition

Purpose

The influence of bone sorbent addition onto distribution of ⁹⁰Sr in artificially contaminated soil was preliminary studied to assess the possibility of biogenic apatite utilization for reduction of ⁹⁰Sr mobility and availability. Simultaneously, the disruption of soil micro- (Cd, Zn, Co, Cu, Cr, and Ni,) and macroelements (Al, Fe, Mn, K, Mg, and Ca) upon Sr contamination and sorbent addition was monitored.

Materials and methods

The model soil was contaminated by inactive Sr, in the form of Sr(NO₃)₂ solution. As a soil additive, sorbent obtained by annealing bovine bones at 400 °C (B400) was applied. Both the uncontaminated and Sr-contaminated soils were mixed with 1, 3, 5, and 10 % of sorbent, suspended in distilled water (initial pH?5; solid/solution ratio, 1:2), and equilibrated for 15 days on a rotary shaker. Solid residues were subjected to modified Tessier five-step sequential extraction analysis, and the amounts of chosen metals in each fraction were determined by inductively coupled plasma–optical emission spectroscopy.

Results and discussion

In the original soil, Sr was mainly found in exchangeable (61 %) and carbonate phase (16 %), whereas after contamination, the content of Sr in exchangeable phase raised to 94 %. With the addition of B400, the decrease in Sr amounts in exchangeable fraction was detected, whereas increase occurred mainly in operationally defined carbonate phase and in the residual. High level of Sr contamination caused the increase in Zn, Ni, Co, Cu, Cd, and Mn and decrease in Ca content in exchangeable phase. Sorbent addition resulted in a migration of these cations to less soluble fractions. This effect was observed even for major soil elements such as Fe, Al, and Mn, regardless of the excessive amounts of Sr in the soil.

Conclusions

Mixing the soil with B400 resulted in reduced Sr mobility and bioavailability. B400 acted as a stabilizing agent for heavy metals, as well. Apatite distinguished selectivity towards heavy metals may interfere with the Sr immobilization and disrupt original cation distribution. Further studies should include more realistic (lower) Sr concentrations in the soil, different soil types, pH, and longer incubation times.     

Effects of 15-year application of municipal wastewater on microbial biomass,fecal pollution indicators,and heavy metals in a Tunisian calcareous soil

Purpose

Water shortage in most countries of the southern Mediterranean basin has led to the reuse of municipal wastewater for irrigation. Despite numerous advantages for soil fertility and crop productivity, recycling wastewater in the soil also has several ecotoxicological and sanitary problems. To evaluate the chronic soil contamination and the cumulative impact of wastewater, we compared seven plot sites irrigated with treated wastewater 1, 2, 7, 9, 13, and 15 years and one nonirrigated taken as control, and these were sampled for soil analysis.

Materials and methods

Soil samples were analyzed for pH, electrical conductivity (EC), total Kjeldahl nitrogen (TKN), total organic matter, and total concentrations of Cu, Zn, Fe, Ni, Pb, and Cd. Microbial biomass and enteric bacteria (fecal coliforms and fecal streptococci) were determined in all soil samples.

Results and discussion

The soil pH values were not consistently affected. Soil salinity, measured as EC, appeared significantly high and proportional to the duration of wastewater irrigation. Also, concentrations of total Ni, Zn, Cu, Pb, and Cd increased significantly (P?≤?0.05) according to the number of irrigation years but are usually under Tunisian standards. The concentration of heavy metals (Ni, Zn, Cu, Pb, and Cd) showed a significant decrease in the soil profile. The microbial biomass carbon (MB_C) is 1.5 times larger in the soil irrigated for 15 years with treated wastewater as compared to the one taken as control. The growth of microorganisms might be explained by the ready source of easily degradable compounds in the oligotrophic soil environment brought about by wastewater irrigation. Soil bacteriological analysis showed that the number of fecal coliforms (FC) and that of fecal streptococci (FS) were affected appreciably (P?≤?0.05) by the duration of wastewater application (number of years) and by the soil depth (0–20, 20–40, and 40–60 cm).

Conclusions

Treated wastewater irrigation led to changes in physicochemical and microbiological soil properties. The magnitude and specificity of these changes significantly correlated with the duration of such practice. It can be concluded, based on these results, that the proper management of wastewater irrigation and periodic monitoring of soil fertility and quality parameters are required to ensure successful, safe, and long-term reuse of wastewater irrigation.     

The influence of compost addition on heavy metal distribution between operationally defined geochemical fractions and on metal accumulation in plant

Purpose

Metal distribution patterns among geochemical fractions are informative for metal phytoavailability. Compost added to polluted soils may adsorb metals on the less phytoavailable fractions. A bioassay experiment was conducted to establish possible correlations between metal concentrations in different soil fractions and metal contents in edible plant parts and to investigate the influence of different compost loads on heavy metal availability to plants.

Materials and methods

Chinese cabbage plants were grown in pots with sandy and clayey soils and soils mixed with different doses of biosolid compost spiked with soluble heavy metal salts (Cd, Cu, and Pb). The metals’ distribution pattern in the soil and mixed samples was determined by sequential extraction procedure (modified BCR protocol). The studied fractions, from most to least bioavailable, were water-extractable (WE), exchangeable-adsorbed (EXC), associated with carbonates and acetic acid-soluble forms (CARB), occluded by reducible (hydro)oxides of Fe and Mn (RO), and associated with organic matter (OM) and a residual fraction (RES). Metal concentrations in soil extracts and in the digested plant tissue were measured by ICP-AES.

Results and discussion

The highest compost doses (72 and 115 Mg ha^?1) enhanced cabbage yield significantly. No excessive phytoaccumulation of metals was observed in plants grown in the clayey soil or its mixtures with compost. The compost dose of 72 Mg ha^?1 was optimal in decreasing Cu accumulation by plants grown in sandy soil, and 28.8 Mg ha^?1 was found to be effective in reducing Cd and Pb uptake. Metals were accumulated in plants primarily from the WE, EXC, and CARB fractions, whereas other fractions decreased phytoaccumulation. Compost addition suppressed heavy metal mobility, but different fractions were active in pollutant sorption, depending on soil type and metal.

Conclusions

Compost addition increased metal proportions in the RO and OM fractions, reducing metal phytoavailability. This is especially important for sandy soils with low adsorption ability and higher vulnerability to metal pollution than clayey soils. A compost dose of 20% v/v (or 28.8 Mg ha^?1) effectively reduced plant accumulation of Cd and Pb. We propose using the first three steps of the modified BCR protocol as a three-step sequential-extraction procedure for the most phytoavailable fractions of heavy metal: WE, EXC, and CARB.     

Evaluation and source identification of trace element contamination of soils in the Qixia lead-zinc mining area,Jiangsu, China

Purpose

The Qixia mine is one of the largest lead-zinc mines in Eastern China and has been operational for approximately 60 years. Source identification for trace element contamination of soils in the Qixia mining area has been lacking. This report details the evaluation and source identification of trace element contamination (including Cu, Zn, Pb, Cd, Hg, Cr, As, and Ni) of soils in this area.

Materials and methods

Thirty-three soil samples from roadsides and fields in the study area were collected and analyzed. The index of geo-accumulation (I _geo) was employed to evaluate contamination. Methods of multivariate statistical analysis were used to determine the probable sources of the pollutants.

Results and discussion

The analysis showed that the levels of contamination ranked in the following order: Cd > Pb/Zn> > As/Cu> > Hg > Cr/Ni. In the sampling area nearest the mine, soil samples collected from roadsides showed much higher levels of contamination than those collected from fields away from the roadways. Trace element contamination decreased as the distance from the mine increased. Contamination extended to a distance of approximately 700 m from mineral transportation routes, with the area of greatest impact at 200 m or less. Multivariate statistical analysis and ore composition data suggest that the Cu, Zn, Pb, Cd, and As found in the soil samples originate from anthropogenic sources. Ni and Cr are considered to be at natural background concentrations.

Conclusions

This study distinguished between natural and anthropogenic sources of trace element contamination in the soils of the Qixia mining area. The contamination of Cu, Zn, Pb, Cd, and As is linked to the mining activities and is likely due to the transportation of ore concentrates and tailings.     

Influence of pH on the release and chemical fractionation of heavy metals in sediment from a suburban drainage stream in an arid mine-based oasis

Purpose

The objectives of this study were to explore the influences of pH on the release of Cu, Zn, Cd, Pb, Ni, and Cr in sediments derived from the upstream, middle, and downstream reaches of Dongdagou stream in Gansu Province, Northwest China, and to examine the fractionation changes of heavy metals in the sediments after reaching their release equilibrium under different pH conditions.

Materials and methods

Sediment samples were obtained using a stainless steel grab sampler to collect the uppermost 10 cm of sediment from the channel bed. The pH-dependent release experiment was conducted in the solid-to-liquid ratio of 1:20 at different pH values (2, 4, 6, 8, 10, and 12) at room temperature. The total Cu, Zn, Cd, Pb, Ni, and Cr concentrations in the sediments were digested using an acid digestion mixture (HNO₃ + HF + HClO₄) in an open system. Metal fractionation of selected sediments was obtained using the Tessier sequential extraction procedure. Heavy metal concentrations in the samples were determined using atomic absorption spectrophotometry.

Results and discussion

The mean concentrations of heavy metals in sediments decreased in the following order: Zn (1676.67 mg kg^?1) > Pb (528.65 mg kg^?1) > Cu (391.34 mg kg^?1) > Cr (53.48 mg kg^?1) > Ni (34.27 mg kg^?1) > Cd (11.53 mg kg^?1). Overall, the solubility of Cu, Zn, Cd, Pb, and Ni decreased with increasing pH, and they were strongly released at pH 2. Moreover, the solubility of Cr increased with increasing pH, and its release was highest at pH 12. After reaching the release equilibrium of heavy metals under different pH conditions, the percentages of organic Cu, Zn, Cd, and Fe-Mn oxyhydroxide Pb decreased, compared to their initial fractions. The residual fractions of Ni and Cr were dominant, regardless of pH.

Conclusions

The average concentrations of Cu, Zn, Cd, and Pb in sediments were highly elevated compared with the soil background values in Gansu Province, China. The results of this pH-dependent release experiment showed that the release behaviors of Cu, Zn, Pb, and Cr followed an asymmetric V-shaped pattern, whereas Cd and Ni followed an irregular L-shaped pattern. The changes in the release of heavy metals in sediments were related to their redistribution between chemical fractionations.

     

Evaluating the necessity for thermal treatment in clay-based metal immobilization techniques as an environmentally acceptable sediment remediation process

Purpose

The objective of this research was to apply the same immobilization (stabilization/solidification) clay-based treatments to sediment contaminated with different metals (Pb, Cd, Ni, Zn, Cu, Cr) with different distributions and availabilities in sediment. We also examined the possibility of using clay as an immobilization agent without the application of thermal treatment, in order to reduce the economic cost of this expensive remediation procedure.

Materials and methods

Clay from a canal in Vojvodina, Republic of Serbia, was used as the immobilization agent in a stabilization/solidification treatment to remediate metal-contaminated sediment. Semi-dynamic and toxicity characteristic leaching tests were conducted to assess the effectiveness of the nonthermal and thermal immobilization treatments with clay, and the long-term leaching behavior of these metals was determined using the following parameters: cumulative percentage of metals leached; diffusion coefficients; leachability indices; and toxicity characteristic leaching test concentration.

Results and discussion

Based on these parameters, both clay-based treatments were effective in immobilizing metals in the contaminated sediment. Results suggest that both heating temperature and clay proportion in the sediment–clay mixture impact the degree of metal immobilization.

Conclusions

Clay-based products are potentially good immobilization materials for metal-contaminated sediments, with the distribution of metals in the original sediment not influencing the efficacy of the treatments. Even without the thermal treatment, the metals were effectively immobilized. The leaching of metals was largely inside the regulatory limits and the treated samples can be regarded as nonhazardous materials. This justifies the choice of not applying the more expensive thermal treatment during remediation, especially when treating sediments containing a mixture of pollutants.     

Effects of biochar on copper immobilization and soil microbial communities in a metal-contaminated soil

Purpose

Copper (Cu) contamination has been increasing in land ecosystems. Biochars (BCs) and arbuscular mycorrhizal fungi (AMF) are known to bind metals, and metallophyte can remove metals from soils. Will BC in combination with AMF contain the Cu uptake by a metallophyte growing in a metal-contaminated soil? The objective of this study was to investigate the effects of BCs on the Cu immobilization and over soil microbial communities in a metal-contaminated soil in the presence of AMF and metallophyte.

Materials and methods

Two BCs were produced from chicken manure (CMB) and oat hull (OHB). A Cu-contaminated sandy soil (338 mg kg^?1) was incubated with CMB and OHB (0, 1, and 5 % w/w) for 2 weeks. Metallophyte Oenothera picensis was grown in pots (500 mL) containing the incubated soils in a controlled greenhouse for 6 months. A number of analyses were conducted after the harvest. These include plant biomass weight, microbial basal respiration, and dehydrogenase activity (DHA), AMF root colonization, spore number, and glomalin production; changes in fungal and bacterial communities, Cu fractions in soil phases, and Cu uptake in plant tissues.

Results and discussion

The BCs increased the soil pH, decreased easily exchangeable fraction of Cu, and increased organic matter and residual fraction of Cu. The BCs provided favorable habitat for microorganisms, thereby increasing basal respiration. The CMB increased DHA by ～62 and ～574 %, respectively, for the low and high doses. Similarly, the OHB increased soil microbial activity by ～68 and ～72 %, respectively, for the low and high doses. AMF root colonization, spore number, and total glomalin-related soil protein (GRSP) production increased by ～3, ～2, and ～3 times, respectively, in soils treated with 1 % OHB. Despite being a metalophyte, O. picensis could not uptake Cu efficiently. Root and shoot Cu concentrations decreased or changed insignificantly in most BC treatments.

Conclusions

The results show that the BCs decreased bioavailable Cu, decreased Cu uptake by O. picensis, improved habitat for microorganisms, and enhanced plant growth in Cu-contaminated soil. This suggests that biochars may be utilized to remediate Cu-contaminated soils.

     

Heavy metal distribution in different soil aggregate size classes from restored brackish marsh,oil exploitation zone,and tidal mud flat of the Yellow River Delta

Purpose

Heavy metal distribution in soils is affected by soil aggregate fractionation. This study aimed to demons trate the aggregate-associated heavy metal concentrations and fractionations in “sandy,” “normal,” and “mud” soils from the restored brackish tidal marsh, oil exploitation zone, and tidal mudflat of the Yellow River Delta (YRD), China.

Materials and methods

Soil samples were sieved into the aggregates of >2, 0.25–2, 0.053–0.25, and <0.053 mm to determine the concentrations of exchangeable (F1), carbonate-bound (F2), reducible (F3), organic-bound (F4), and residual fraction (F5) of Cd, Cr, Cu, Ni, Pb, and Zn.

Results and discussion

The 0.25–2 mm aggregates presented the highest concentrations but the lowest mass loadings (4.23–12.18 %) for most metal fractions due to low percentages of 0.25–2 mm aggregates (1.85–3.12 %) in soils. Aggregates <0.053 mm took majority mass loadings of metals in sandy and normal soils (62.04–86.95 %). Most soil aggregates had residual Cr, Cu, Ni, Zn, and reducible Cd, Pb dominated in the total Cd, Cr, Cu, Ni, Pb, and Zn concentrations. Sandy soil contained relatively high F4, especially of Cu (F4) in 0.25–2 mm aggregates (10.22 mg kg^?1), which may relate to significantly high organic carbon contents (23.92 g kg^?1, P?<?0.05). Normal soil had the highest total concentrations of metals, especially of Cu, Ni, and Pb, which was attributed to the high F3 and F5 in the <0.053 mm aggregates. Although mud soil showed low total concentrations of heavy metals, the relatively high concentrations of bioavailable Cd and Cu resulted from the relatively high Cd (F2) and Cu (F2) in the >2 mm aggregates indicated contribution of carbonates to soil aggregation and metal adsorption in tidal mud flat.

Conclusions

Soil type and aggregate distribution were important factors controlling heavy metal concentration and fractionation in YRD wetland soil. Compared with mud soil, normal soil contained increased concentrations of F5 and F3 of metals in the 0.053–0.25 mm aggregate, and sandy soil contained increased concentrations of bioavailable and total Cr, Ni, and Zn with great contribution of mass loadings in the <0.053 mm aggregate. The results of this study suggested that oil exploitation and wetland restoration activities may influence the retention characteristics of heavy metals in tidal soils through variation of soil type and aggregate fractions.

     

Micro/nanostructured hydroxyapatite structurally enhances the immobilization for Cu and Cd in contaminated soil

Purpose

The presence of high copper (Cu) and cadmium (Cd) contamination in soils around mining areas has raised serious health concerns. Improving hydroxyapatite (HAP) adsorption capacity for Cu and Cd is important if its application potential in heavily contaminated soils is to expand.

Materials and methods

The micro/nanostructured HAP (mnHAP) was synthesized using a template-induced method to improve the HAP immobilization of Cu and Cd in contaminated soils. Commercial and synthetic HAPs were evaluated as amendments in Cu and Cd remediation tests with 1.5 and 3.0 % addition level for 90 days, and soils without HAP materials (0.0 %) were designated as the controls; each treatment was repeated three times. The materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N₂ adsorption, and scanning electron microscopy (SEM)-energy-dispersive spectra (EDS) and then quantitatively determined the Cu and Cd contents by inductively coupled plasma (ICP) and inductively coupled plasma mass spectrometry (ICP-MS).

Results and discussion

The mnHAP was more effective in immobilizing Cu and Cd than the two commercial HAPs. After treatment with mnHAP at the 3.0 % addition level for 90 days, the contaminated soils showed 55.2 and 84.8 % reductions in Cu and Cd concentrations in the toxicity characteristic leaching procedure (TCLP) leaching procedure, respectively. The experimental data indicated that the enhanced Cu and Cd immobilization by mnHAP was due to the increases of surface area and the improvement of structure and newly introduced carboxylate groups on its surface.

Conclusions

These findings show that regulating the structure and surface properties of HAP can enhance Cu and Cd immobilization in soils.

     

Eisenia fetida growth inhibition by amended activated carbon causes less bioaccumulation of heavy metals

Purpose

Activated carbons (ACs) were applied to evaluate the effects of surface oxidation on bioavailability and bioaccumulation of cadmium (Cd) and copper (Cu) in freshwater sediment along with Eisenia fetida biomass change.

Materials and methods

A modified sequential extraction procedure was conducted to measure the changes in bioavailable fractions of heavy metals 6 weeks after the addition of nitric acid-oxidized AC. Bioaccumulation of heavy metals in E. fetida was analyzed after 2 weeks of exposure to AC-amended contaminated sediments. Changes in biomass of earthworms caused by AC amendments were observed over 2 weeks of exposure to clean sand.

Results and discussion

Surface oxidation of AC caused little impact on AC surface properties except for oxygen contents leading to enhanced sorption capacity for heavy metals. Bioavailable fractions of the heavy metals increased after 6 weeks, and less was bioavailable with various ACs than without AC. The earthworms were exposed to the sediments mixed with ACs for 6 weeks. After 2 weeks of exposure, bioaccumulation of Cd and Cu decreased drastically. More than 76 % of Cd and 80 % of Cu reductions were observed with each type and dose of AC. Weight loss of E. fetida incubated in clean sand for 13 days after AC amendments was observed, but was not affected by surface oxidation.

Conclusions

Inhibited growth of E. fetida due to AC could be responsible for the reduced bioaccumulation of Cd and Cu in the earthworms as AC inhibited the movement of earthworms, leading to less bioturbation and decreased consumption of nutrients.     

Biochars immobilize soil cadmium, but do not improve growth of emergent wetland species Juncus subsecundus in cadmium-contaminated soil

Purpose

An addition of biochar mixed into the substrate of constructed wetlands may alleviate toxicity of metals such as cadmium (Cd) to emergent wetland plants, leading to a better performance in terms of pollutant removal from wastewater. The objective of this study was to investigate the impact of biochars on soil Cd immobilization and phytoavailability, growth of plants, and Cd concentration, accumulation, and translocation in plant tissues in Cd-contaminated soils under waterlogged conditions.

Materials and methods

A glasshouse experiment was conducted to investigate the effect of biochars derived from different organic sources (pyrolysis of oil mallee plants or wheat chaff at 550 °C) with varied application amounts (0, 0.5, and 5 % w/w) on mitigating Cd (0, 10, and 50 mg kg^?1) toxicity to Juncus subsecundus under waterlogged soil condition. Soil pH and CaCl₂/EDTA-extractable soil Cd were determined before and after plant growth. Plant shoot number and height were monitored during the experiment. The total root length and dry weight of aboveground and belowground tissues were recorded. The concentration of Cd in plant tissues was determined.

Results and discussion

After 3 weeks of soil incubation, pH increased and CaCl₂-extractable Cd decreased significantly with biochar additions. After 9 weeks of plant growth, biochar additions significantly increased soil pH and electrical conductivity and reduced CaCl₂-extractable Cd. EDTA-extractable soil Cd significantly decreased with biochar additions (except for oil mallee biochar at the low application rate) in the high-Cd treatment, but not in the low-Cd treatment. Growth and biomass significantly decreased with Cd additions, and biochar additions did not significantly improve plant growth regardless of biochar type or application rate. The concentration, accumulation, and translocation of Cd in plants were significantly influenced by the interaction of Cd and biochar treatments. The addition of biochars reduced Cd accumulation, but less so Cd translocation in plants, at least in the low-Cd-contaminated soils.

Conclusions

Biochars immobilized soil Cd, but did not improve growth of the emergent wetland plant species at the early growth stage, probably due to the interaction between biochars and waterlogged environment. Further study is needed to elucidate the underlying mechanisms.     

Comparing chemical-enhanced washing and waste-based stabilisation approach for soil remediation

Purpose

This study aimed to compare the effectiveness of chemical-enhanced soil washing (with chelating agents, humic substances and inorganic acids) and soil stabilisation by inorganic industrial by-products (coal fly ash, acid mine drainage sludge and zero-valent iron) and organic resource (lignite) for timber treatment site remediation.

Materials and methods

Both remediation options were assessed in terms of extraction/leaching kinetics and residual leachability (toxicity characteristic leaching procedure, TCLP) of the major risk drivers, i.e. Cu and As.

Results and discussion

In chemical-enhanced soil washing, chelating agents only minimised the Cu leachability. Humic substances were ineffective while inorganic acids reduced the As leachability to the detriment of the soil quality. For the waste-stabilised soil, the short-term leaching potential (72 h) and long-term TCLP leachability (9 months) revealed that Fe-/Al-/Ca-rich AMD sludge and coal fly ash sequestered As through adsorption and (co-)precipitation, while carbonaceous lignite stabilised Cu with oxygen-containing functional groups. The short-term and long-term leaching of Cu and As into the soil solution was negligible in the presence of the waste materials. However, the waste-stabilised soil did not maintain sufficient Cu stability in the TCLP tests, in which acetate buffer induced significant mineral dissolution of the waste materials.

Conclusions

These results suggest that chelant-enhanced washing (significant reduction of Cu leachability) may be augmented with subsequent stabilisation with inorganic waste materials (effective control of As leachability), thus minimising the environmental risks of both Cu (heavy metal) and As (metalloid) while preserving the reuse value of the soil. Additional tests under field-relevant conditions are required to provide a holistic performance evaluation.     

Fractionation of Cd and Zn in Cd-contaminated soils amended by sugarcane waste products from an ethanol production plant

Purpose

Sugarcane waste products (boiler ash, filter cake, and vinasse) from an ethanol production plant were used as soil amendments by adding 3 % (w/w) in single and/or in combination, with a research focus towards stabilization of cadmium (Cd) and zinc (Zn) in contaminated soils. The objective of this laboratory study was to evaluate the effects of adding these sugarcane waste products on bioavailability of Cd and Zn over time (aging) in Cd- and Zn-contaminated agricultural soils of Thailand.

Materials and methods

Two agricultural contaminated soils of low (<3 mg kg^?1) and high (10–15 mg kg^?1) Cd concentrations were collected from Tak Province, Northwest Thailand. Fourteen treatments were sampled at 2-week intervals for 84 days for metal bioavailability using BCR extraction procedures (proposed by The Standards, Measurements and Testing Programme of the European Union, SM&T) that determined exchangeable (BCR1), reducible (BCR2), oxidizable (BCR3), and residual (BCR4) fractions, and total concentration was determined using aqua regia digestion and microwave digestion.

Results and discussion

Cd was potentially bioavailable, predominantly in exchangeable (BCR1) and reducible (BCR2) fractions, while the higher contribution of Zn was more prevalent in refractory fractions (BCR2 and BCR4). Aging had an influence on fractionation of Cd and Zn, most notably in the first two fractions (BCR1 and BCR2) of BCR sequential extraction, which resulted in reduction of exchangeable Cd during the first few weeks of incubation (T?=?0 to 28 days). At the end of pot experiment, the exchangeable Cd fraction in the low Cd (LCdS) soil was reduced from 2.3 to 4.7 % and 9.4 to 39.9 % in low and high Cd (HCdS)-contaminated soils, respectively, as compared to nonamended soils.

Conclusions

The observed reduction in exchangeable Cd (BCR1) in the amended soils at the 3 % (w/w) application rate, the low total metal concentrations, and the significant amount of essential plant nutrients (N, P, and K) within these waste products highlight the benefits of amending metal-rich soils with them.     

Pilot-scale counter-current acid leaching process for Cu,Pb, Sb,and Zn from small-arms shooting range soil

Purpose

The main objective of this study was to evaluate the potential of a counter-current leaching process (CCLP) on 14 cycles with leachate treatment at the pilot scale for Pb, Cu, Sb, and Zn removal from the soil of a Canadian small-arms shooting range.

Materials and methods

The metal concentrations in the contaminated soil were 904?±?112 mg Cu kg^–1, 8,550?±?940 mg Pb kg^–1, 370?±?26 mg Sb kg^–1, and 169?±?14 mg Zn kg^–1. The CCLP includes three acid leaching steps (0.125 M H₂SO₄?+?4 M NaCl, pulp density (PD)?=?10 %, t?=?1 h, T?=?20 °C, total volume?=?20 L). The leachate treatment was performed using metal precipitation with a 5-M NaOH solution. The treated effluent was reused for the next metal leaching steps.

Results and discussion

The average metal removal yields were 80.9?±?2.3 % of Cu, 94.5?±?0.7 % of Pb, 51.1?±?4.8 % of Sb, and 43.9?±?3.9 % of Zn. Compared to a conventional leaching process, the CCLP allows a significant economy of water (24,500 L water per ton of soil), sulfuric acid (133 L H₂SO₄ t^–1), NaCl (6,310 kg NaCl t^–1), and NaOH (225 kg NaOH t^–1). This corresponds to 82 %, 65 %, 90 %, and 75 % of reduction, respectively. The Toxicity Characteristic Leaching Procedure test, which was applied on the remediated soil, demonstrated a large decrease of the lead availability (0.8 mg Pb L^–1) in comparison to the untreated soil (142 mg Pb L^–1). The estimated total cost of this soil remediation process is 267 US$ t^–1.

Conclusions

The CCLP process allows high removal yields for Pb and Cu and a significant reduction in water and chemical consumption. Further work should examine the extraction of Sb from small-arms shooting range.     

Effect of the size of variable charge soil particles on cadmium accumulation and adsorption

Purpose

The size of soil particles strongly affects the accumulation and adsorption of heavy metals which partly controls the co-transport of heavy metals by soil colloids. However, the effect of the size of soil particles on the accumulation and adsorption of heavy metals in the colloidal dimension has seldom been studied. In this study, variable charge soils were selected and separated into five size fractions to elucidate the effect of the size of soil particles on Cd accumulation and adsorption.

Materials and methods

Five soil particle size fractions (>10, 10–1, 1–0.45, 0.45–0.2 and <0.2 μm) were obtained from Cd-contaminated soil by natural sedimentation and fractional centrifugation. The concentrations and species of Cd were measured in various sized soil particles. Batch adsorption experiments of Cd on the obtained soil particles were conducted under different pH values and concentrations of NaCl.

Results and discussion

Generally, the concentration of Cd increased with decreasing soil particle sizes, and the Cd proportion of exchangeable and carbonate fraction decreased from 43.84 to 17.75% with decreasing particle size. The soil particles with a size of 10–1 and <0.2 μm possessed a stronger adsorption ability than the other fractions in most cases. Moreover, the Cd adsorption capacities of the soil particles increased with increasing pH values and decreasing concentrations of NaCl, especially for soil particles containing more organic matter (OM) and variable charge minerals.

Conclusions

Smaller soil particles are more capable of accumulating Cd and make Cd more stable. The adsorption capability of Cd is negatively related to the particle size and NaCl concentration and is positively related to the pH. The effects of the size of variable charge soil particles on Cd accumulation and adsorption are attributed to the differences in the physicochemical properties among various soil particle size fractions. This study contributes to the understanding of the co-transport of heavy metals in soil by soil colloids.