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.

     

Evaluation of palygorskite for remediation of Cd-polluted soil with different water conditions

Purpose

The study aimed at comparing the effects of different water managements on soil Cd immobilization using palygorskite, which was significant for the selection of reasonable water condition.

Materials and methods

Field experiment was taken to discuss the in situ remediation effects of palygorskite on Cd-polluted paddy soils, under different water managements, using a series of variables, including pH and extractable Cd in soils, plant Cd, enzyme activity, and microorganism number in soils.

Results and discussion

In control group, the pH in continuous flooding was the highest under three water conditions, and compared to conventional irrigation, continuous flooding reduced brown rice Cd by 37.9%, and brown rice Cd in wetting irrigation increased by 31.0%. In palygorskite treated soils, at concentrations of 5, 10, and 15 g kg^?1, brown rice Cd reduced by 16.7, 44.4, and 55.6%; 13.8, 34.5, and 44.8%; and 13.1, 36.8, and 47.3% under continuous flooding, conventional irrigation, and wetting irrigation (p < 0.05), respectively. The enzyme activity and microbial number increased after applying palygorskite to paddy soils.

Conclusions

Continuous flooding was a good candidate as water management for soil Cd stabilization using palygorskite. Rise in soil enzyme activity and microbial number proved that ecological function regained after palygorskite application.

     

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.

     

Rhizosphere effects of <Emphasis Type="Italic">Populus euramericana</Emphasis> Dorskamp on the mobility of Zn,Pb and Cd in contaminated technosols

Purpose

This study aimed at investigating the rhizosphere effects of Populus euramericana Dorskamp on the mobility of Zn, Pb and Cd in contaminated technosols from a former smelting site.

Materials and methods

A rhizobox experiment was conducted with poplars, where the plant stem cuttings were grown in contaminated technosols for 2 months under glasshouse conditions. After plant growth, rhizosphere and bulk soil pore water (SPW) were sampled together. SPW properties such as pH, dissolved organic carbon (DOC) and total dissolved concentrations of Zn, Pb and Cd were determined. The concentrations of Zn, Pb and Cd in plant organs were also determined.

Results and discussion

Rhizosphere SPW pH increased for all studied soils by 0.3 to 0.6 units compared to bulk soils. A significant increase was also observed for DOC concentrations regardless of the soil type or total metal concentrations, which might be attributed to the plant root activity. For all studied soils, the rhizosphere SPW metal concentrations decreased significantly after plant growth compared to bulk soils which might be attributed to the increase in pH and effects of root exudates. Zn, Pb and Cd accumulated in plant organs and the higher metal concentrations were found in plant roots compared to plant shoots.

Conclusions

The restricted transfer of the studied metals to the plant shoots confirms the potential role of this species in the immobilization of these metals. Thus, P. euramericana Dorskamp can be used for phytostabilization of technosols.

     

Chicken-manure-derived biochar reduced bioavailability of copper in a contaminated soil

Purpose

Copper (Cu) contamination has been increasing in land ecosystems due to economic development activities. Excessive amount of Cu in soils is toxic to both plants and microorganisms. Biochar (BC) is known to immobilize soil Cu. The objectives of this research were to investigate the effects of chicken-manure-derived BC (CMB) on Cu immobilization, and growth of native metallophyte Oenothera picensis in a Cu-contaminated soil.

Materials and methods

A Cu-contaminated sandy soil (338 mg Cu kg^?1) was spiked and equilibrated with additional Cu (0, 100, and 500 mg Cu kg^?1). The spiked soil was then amended with CMB (0, 5, and 10 % w/w) and incubated for 2 weeks. The metallophyte was grown on these treatments under greenhouse conditions for 3 months. Pore water solutions were collected from the plant pots every 30 days. After the harvest, soil and pore water pH, soil Cu fractions, pore water Cu concentration, soil microbial activity, plant biomass weight, and Cu concentration in plant parts were determined.

Results and discussion

The CMB increased the pH of soils and soil pore water, and probably also soil major nutrients. It reduced the exchangeable fraction of Cu but increased its organic matter and residual fractions. At the same time, it decreased the Cu concentration in the soil pore water. The CMB increased basal respiration and dehydrogenase activity. The CMB application produced up to three and seven times more root and shoot biomass, respectively. In addition, shoots accumulated lesser Cu than control but roots did more. Plants survived in soil that was spiked with 500 mg Cu kg^?1, only when CMB dose was 10 %.

Conclusions

The CMB affected the Cu uptake in plant by altering the mobility, bioavailability, and spatial distribution of Cu in soils. The increase in available nutrients and decrease in Cu toxicity facilitated plant growth. The increased microbial activity probably also promoted the plant growth and reduced the Cu bioavailability. Therefore, CMB can be used 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.

     

Dry cultivation enhances cadmium solubility in contaminated soils but minimizes cadmium accumulation in a leafy vegetable

Purpose

Water management has a strong influence on Cd solubility in agricultural soils, affecting Cd uptake in crops. In the process, sulfur interaction with other metals such as zinc may play an important role. A pot experiment was carried out to investigate the effects of water management coupled with zinc and sulfate amendment on Cd uptake by the leafy vegetable amaranth with a strong Cd accumulation tendency in its edible parts.

Materials and methods

The soils were amended with Cd, Cd+SO₄ and Cd+SO₄+Zn with no amendment as control. Then, the soils were flooded for 1 month, after which amaranth was grown with soil kept saturated (wet cultivation). In the succeeding planting, soils were tilled to aeration condition under which amaranth was grown again (dry cultivation). Soil and crop samples were collected and analysed for various parameters.

Results and discussion

The readily exchangeable quantities of Cd and Zn in the soil decreased under wet cultivation, increasing again under dry cultivation but to levels lower than those in the initial soil. Wet cultivation enhanced plant Cd concentration but reduced Zn accumulation compared to dry cultivation. Zn bioavailability was strongly affected by soil water status but failed to reduce Cd uptake by amaranth. Irreversible or slowly reversible changes occurred in Cd and Zn solubility and phytoavailability as soil water-saturated status was altered by periodic flooding events.

Conclusions

Dry cultivation with lower soil water content ensured high production with low Cd in the edible part of this leaf vegetable and so remains the recommended irrigation regime.

     

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.

     

Potentially toxic elements in the riparian soils of the Sava River

Purpose

Riparian zone contamination is a growing problem for several European catchments due to high anthropogenic pressures. This study investigates As, Cd, Cr, Cu, Ni, Pb, and Zn concentrations in the Sava River riparian zone, characterized by wide agricultural areas, various geological substrates, and different types of industrial pollution. The accumulation and mobility of these elements were studied because they are listed as priority substances in the Water Framework Directive and environmental objectives for surface waters.

Materials and methods

Sampling was performed during the sampling campaign of the EU 7th FW-funded GLOBAQUA project in September 2015 during a low-water event. Soil samples were collected along the Sava River at 12 selected sampling sites, from a depth of 0–30 cm, at a distance of 10–15 m from the river bank. The extent of pollution was estimated by determining total and readily soluble element concentrations in the soils. Potential ecological risk and the source of the selected elements in the soils was determined using the enrichment factor (EF), potential ecological risk index (RI), and statistical methods such as the principal component analysis (PCA) and multiple linear regression analysis (MLRA).

Results and discussion

This study showed that concentrations of the selected elements increase along the Sava. In terms of origin, PCA and MLRA indicated that Cr and Ni in soils are predominantly lithogenic, while As, Cd, Pb, and Zn are both lithogenic and anthropogenic (ore deposits, industry, and agriculture). PCA singled out Cu since its origin in soil is most probably from specific point-source pollution. EF was generally minor to moderate for most of the examined elements, apart from Cu, for which the EF was significant at one sampling site. Overall ecological risk (RI) fell within the low-risk category for most sites, apart from Belgrade sampling site (BEO), where high total Cd content affected individual and overall ecological risk indicators, indicating Cd could represent a considerable ecological risk for the downstream riparian zone.

Conclusions

At downstream sites, there was a noticeable increase in PTE content, with Cd, Cr, Ni, and Zn exceeding the proposed threshold values for European soils, indicating rising contamination in riparian soils. In terms of the ecological risk, only Cd could pose a potential ecological threat for the downstream riparian zone.

     

Total petroleum hydrocarbons and heavy metals in road-deposited sediments in Tijuana,Mexico

Purpose

A study was carried out to evaluate the concentration of heavy metals (Pb, Cu, Cr, Cd, and Hg) and total petroleum hydrocarbons (TPH) in road-deposited sediments (RDS) from Tijuana, Mexico, and identify their possible sources.

Materials and methods

Thirty RDS samples were randomly collected during the dry season using a brush and dustpan and classified according to construction material, traffic intensity, and land use. Soil samples were collected from a nonurban area and their concentrations were used as background values. For TPH, the samples were quantified gravimetrically after Soxhlet extraction, whereas heavy metals were extracted by acid digestion and their concentrations were measured by atomic absorption spectrometry.

Results and discussion

The mean TPH concentrations for RDS were 4208 mg kg^?1 and ranged from 1186 to 9982 mg kg^?1. For heavy metals, mean concentrations were 31.8, 50.2, 17.1, 0.1, and 0.1 mg kg^?1 for Pb, Cu, Cr, Cd, and Hg, respectively. The Igeo results showed that RDS from Tijuana are moderately to strongly polluted with Pb and Cu and moderately polluted with Cr. Principal component analysis (PCA) showed that Pb, Cu, and Cr could have their origin in tire wear, brake pads, bearings, and bushings.

Conclusions

The findings of this study revealed that RDS from Tijuana are polluted with TPH and heavy metals and that their principal sources are anthropogenic activities.

     

Distribution and fractionation of cadmium in soil aggregates affected by earthworms (<Emphasis Type="Italic">Eisenia fetida</Emphasis>) and manure compost

Purpose

The objectives of this study were (1) to investigate the effects of manure compost and earthworms on Cd mobility in Cd-contaminated soil, (2) to test whether the bioturbation of earthworms reduces the immobilization effect of the manure compost when they are combined, and (3) to explore the distribution of Cd in aggregates formed by earthworms with corresponding fractionation analysis.

Materials and methods

A laboratory experiment was conducted to evaluate the effect of either or both application of manure compost and the earthworms Eisenia fetida into cadmium historically contaminated soil on cadmium mobility. Soil characteristics and metal concentrations in earthworms and soil were measured, and soil aggregates in the mesocosms were separated for Cd fraction analysis based on four steps sequential extraction.

Results and discussion

Manure compost reduced mobile Cd based on CaCl₂ extraction and Toxicity Characteristic Leaching Procedure (TCLP) test by 60–95 and 25–30 %, respectively. However, earthworm application alone increased Cd mobility by 9–15 %. Besides, in the presence of manure compost, earthworms further immobilized cadmium to a slight extent. The interaction effect of manure compost and earthworms combined on Cd immobilization suggested that earthworms promoted the formation of large macroaggregates (>2 mm) and the redistribution of Cd concentration in soil aggregates. Additionally, earthworms reduced carbonate fraction of Cd from 42.3–49.6 to 6.3–19.5 % in different aggregates, respectively. And, residual fraction of Cd increased from 33.9–42.2 to 63.9–77.5 % simultaneously. The results may be due to the thorough mixture of phosphates and organic matter with cadmium during bioturbation on account of the available form of phosphorus, nitrogen, and cadmium changing to the more recalcitrant form.

Conclusions

Manure compost addition increased the soil pH, phosphorus, nitrogen, and organic carbon content, and decreased Cd mobility. The application of earthworms and manure compost combined exhibited higher efficiency for cadmium immobilization, which can be used for Cd remediation due to the redistribution of Cd concentration in soil aggregates and the transformation of soluble Cd to the residual precipitate fraction.

     

Biochar-induced changes in soil properties affected immobilization/mobilization of metals/metalloids in contaminated soils

Purpose

Remediation of metal contaminated soil with biochar is attracting extensive interest in recent years. Understanding the significance of variable biochar properties and soil types helps elucidating the meticulous roles of biochar in immobilizing/mobilizing metals/metalloids in contaminated soils.

Materials and methods

Six biochars were produced from widely available agricultural wastes (i.e., soybean stover, peanut shells and pine needles) at two pyrolysis temperatures of 300 and 700 °C, respectively. The Pb-, Cu-, and Sb-contaminated shooting range soils and Pb-, Zn-, and As-contaminated agricultural soils were amended with the produced biochars. The mobility of metals/metalloids was assessed by the standard batch leaching test, principal component analysis and speciation modeling.

Results and discussion

The changes in soil properties were correlated to feedstock types and pyrolysis temperatures of biochars based on the principal component analysis. Biochars produced at 300 °C were more efficient in decreasing Pb and Cu mobility (>93 %) in alkaline shooting range soil via surface complexation with carboxyl groups and Fe-/Al-minerals of biochars as well as metal-phosphates precipitation. By contrast, biochars produced at 700 °C outperformed their counterparts in decreasing Pb and Zn mobility (100 %) in acidic agricultural soil by metal-hydroxides precipitation due to biochar-induced pH increase. However, Sb and As mobility in both soils was unfavorably increased by biochar amendment, possibly due to the enhanced electrostatic repulsion and competition with phosphate.

Conclusions

It is noteworthy that the application of biochars is not equally effective in immobilizing metals or mobilizing metalloids in different soils. We should apply biochar to multi-metal contaminated soil with great caution and tailor biochar production for achieving desired outcome and avoiding adverse impact on soil ecosystem.

     

Nitrogen transformation rates and N<Subscript>2</Subscript>O producing pathways in two pasture soils

Purpose

Better understanding of N transformations and the regulation of N₂O-related N transformation processes in pasture soil contributes significantly to N fertilizer management and development of targeted mitigation strategies.

Materials and methods

¹⁵N tracer technique combined with acetylene (C₂H₂) method was used to measure gross N transformation rates and to distinguish pathways of N₂O production in two Australian pasture soils. The soils were collected from Glenormiston (GN) and Terang (TR), Victoria, Australia, and incubated at a soil moisture content of 60% water-filled pore space (WFPS) and at temperature of 20 °C.

Results and discussion

Two tested pasture soils were characterized by high mineralization and immobilization turnover. The average gross N nitrification rate (n_tot) was 7.28 mg N kg^?1 day^?1 in TR soil () and 5.79 mg N kg^?1 day^?1 in GN soil. Heterotrophic nitrification rates (n_h), which accounting for 50.8 and 41.9% of n_tot, and 23.4 and 30.1% of N₂O emissions in GN and TR soils, respectively, played a role similar with autotrophic nitrification in total nitrification and N₂O emission. Denitrification rates in two pasture soils were as low as 0.003–0.004 mg N kg^?1 day^?1 under selected conditions but contributed more than 30% of N₂O emissions.

Conclusions

Results demonstrated that two tested pasture soils were characterized by fast N transformation rates of mineralization, immobilization, and nitrification. Heterotrophic nitrification could be an important NO₃^?–N production transformation process in studied pasture soils. Except for autotrophic nitrification, roles of heterotrophic nitrification and denitrification in N₂O emission in two pasture soils should be considered when developing mitigation strategies.

     

Effects of phosphate on trace element accumulation in rice (<Emphasis Type="Italic">Oryza sativa</Emphasis> L.): a 5-year phosphate application study

Purpose

Phosphate (P) fertilizers are being widely used to increase crop yield, especially in P-deficient soils. However, repeated applications of P could influence trace element bioaccumulation in crops. The effects of 5-year P enrichment on trace element (Cu, Zn, Cd, Pb, As, and Hg) accumulation in Oryza sativa L. were thus examined.

Materials and methods

Two paddy soils with different initial P availabilities were amended with and without P fertilizer from 2009 to 2013. Trace elements and P levels in rice and soils were analyzed.

Results and discussion

In soil initially with limited P, P amendment enhanced grain Pb, As, and Hg concentrations by 1.8, 1.5, and 1.4-fold, respectively, but tended to decrease the grain Cd level by 0.73-fold, as compared to the control. However, in soil initially with sufficient P, P amendment tended to reduce accumulation of all examined elements in rice grain.

Conclusions

Phosphate amendment in initially P-limited and P-sufficient soils had different effects on trace element availability in soil (as reflected by extractable element) and plant physiology (growth and metal translocation), resulting in contrasting patterns of trace element accumulation in rice between the two types of soils. Our study emphasized the necessity to consider the promoting effects of P on Pb, As, and Hg accumulation in grain in initial P-deprived soil.

     

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.

     

Response of CaCl<Subscript>2</Subscript>-extractable heavy metals,polychlorinated biphenyls,and microbial communities to biochar amendment in naturally contaminated soils

Purpose

Biochar can be used to reduce the bioavailability and leachability of heavy metals, as well as organic pollutants in soils through adsorption and other physicochemical reactions. The objective of the study was to determine the response of microbial communities to biochar amendment and its influence on heavy metal mobility and PCBs (PCB52, 44, 101, 149, 118, 153, 138, 180, 170, and 194) concentration in application of biochar as soil amendment.

Materials and methods

A pot (macrocosm) incubation experiment was carried out with different biochar amendment (0, 3, and 6 % w/w) for 112 days. The CaCl₂-extractable concentration of metals, microbial activities, and bacterial community were evaluated during the incubation period.

Results and discussion

The concentrations of 0.01 M CaCl₂-extractable metals decreased (p?>?0.05) by 12.7 and 20.5 % for Cu, 5.0 and 15.6 % for Zn, 0.2 and 0.5 % for Pb, and 1.1 and 8.9 % for Cd, in the presence of 3 and 6 % of biochar, respectively, following 1 day of incubation. Meanwhile, the total PCB concentrations decreased from 1.23 mg kg^?1 at 1 day to 0.24 mg kg^?1 at 112 days after 6 % biochar addition, representing a more than 60 % decrease relative to untreated soil. It was also found out that biochar addition increased the biological activities of catalase, phosphatase, and urease activity as compared with the controls at the same time point. Importantly, the Shannon diversity index of bacteria in control soils was 3.41, whereas it was 3.69 and 3.88 in soils treated with 3 and 6 % biochar soil. In particular, an increase in the number of populations with the putative ability to absorb PCB was noted in the biochar-amended soils.

Conclusions

The application of biochar to contaminated soils decreased the concentrations of heavy metals and PCBs. Application of biochar stimulated Proteobacteria and Bacteroides, which may function to absorb soil PCB and alleviate their toxicity.

     

Characterization of soil physico-chemical parameters and limitations for revegetation in serpentine quarry soils (NW Spain)

Purpose

Quarrying activities in areas with serpentinized rocks may have a negative impact on plant growth. Quarry soils generally offer hostile environments for plant growth due to their low-nutrient availability, low organic matter, and high-trace metal content.

Materials and methods

In order to determine the factors that can limit plant revegetation, this study was carried out in two serpentine quarries in Galicia (NW Spain): one abandoned in 1999 and the other still active.

Results and discussion

The results show that in soils developed in the abandoned quarry, the limitations for revegetation were: moderate alkaline pH (7.87–8.05), strong Ca/Mg (<1) imbalance, low N (<0.42 mg kg^?1) and P (<2 mg kg^?1) content, and high total heavy-metal content (Co 76–147 mg kg^?1; Cr 1370–2600 mg kg^?1; and Ni 1340–2040 mg kg^?1). The limitations were much less intense in the soils developed in the substratum in the active quarry, which were incipient soils poorly developed and permanently affected by the quarrying activity.

Conclusions

Restoration work should be geared toward establishing a stable diverse vegetation cover, including serpentinophile species, which would provide the necessary modifications to correct nutritive imbalances and improve soil quality.

     

Biosynthesis of schwertmannite by <Emphasis Type="Italic">Acidithiobacillus ferrooxidans</Emphasis> and its application in arsenic immobilization in the contaminated soil

Purpose

Soil contamination with arsenic (As) is an increasingly worldwide concern. Immobilization is a potentially reliable, cost-effective technique for the reclamation of As-contaminated soils. The aim of this study is to develop new soil amendments with high As immobilization efficiency, cost-effective, environmental-friendly, and without soil acidification for As-contaminated soil remediation.

Materials and methods

Biosynthesis of schwertmannite by Acidithiobacillus ferrooxidans has been conducted, and two types of biogenetic schwertmannites SCH and A-SCH were prepared and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), etc. The A-SCH was formed through pretreating SCH by acidic and alkaline activation. The potential of SCH and A-SCH in As immobilization in contaminated soil was evaluated. The effect of ferrous sulfate and A-SCH on soil pH and immobilization of NaHCO₃-extractable As were also investigated for comparison.

Results and discussion

The chemical formula of SCH and A-SCH can be expressed as Fe₈O₈(OH)_4.89(SO₄)_1.55 and Fe₈O₈(OH)_5.19(SO₄)_1.41, respectively. Compared to SCH, A-SCH exhibits much higher specific surface area of 74.99 m² g^?1 and contains more hydroxyl groups and inner-sphere sulfate complexes. Immobilization efficiency of water-soluble As above 99.5 % can be achieved with A-SCH dosage of 5 % and SCH dosage of 10 %, respectively. The immobilization percentages of NaHCO₃-extractable As increased from 31.5 to 90.4 % and from 40.2 to 93.8 % with increasing dosage from 0.5 to 10 wt % for SCH and A-SCH, respectively. In general, both SCH and A-SCH immobilize As in contaminated soil effectively, and the immobilization performance of A-SCH was better than that of SCH, especially at lower dosage.

Conclusions

Biogenetic schwertmannite could be used as a potential effective soil amendment for As immobilization in contaminated soil. Our findings in this study also have important implications for in situ immobilization of As in contaminated soils, especially the soils related to acidic iron and sulfate-rich environments.

     

Mixed chelators of EDTA,GLDA, and citric acid as washing agent effectively remove Cd,Zn, Pb,and Cu from soils

Purpose

Soil washing with chelators is a viable treatment alternative for remediating multi-contaminated soils. The aim of this study was to investigate the removal efficiencies of Cd, Zn, Pb, and Cu in alkaline and acid multi-metal-contaminated soils by washing with the mixed chelators (MC).

Materials and methods

The batch experiments were carried out to evaluate the removal efficiencies of heavy metals in contaminated soils by the MC with different molar ratios of EDTA, GLDA, and citric acid, and evaluated the washing factors, including contact time, pH, MC concentration, and single and multiple washings at the same MC dose, on the removal efficiencies.

Results and discussion

Results showed that the removal efficiencies for Cd, Zn, Pb, and Cu by the MC (the molar ratio of EDTA, GLDA, and citric acid was 1:1:3) were as much as those of the only EDTA washing from both soil at the same application dose of total chelators; moreover, the application dose of EDTA decreased by 80%. For the alkaline-contaminated soil, the removal efficiencies of Cd, Zn, Pb, and Cu decreased with the increasing of the solution pH, which was opposite to acid-contaminated soil. This was attributed to that the metal-ligand complex could be obviously re-adsorbed on the soil surface sites, particularly in low pH values. The removal efficiencies of Cd, Zn, Pb, and Cu depended on MC concentration. A higher MC concentration led to a more effective removal of Cd, Zn, Pb, and Cu in alkaline-contaminated soil; however, their changes were slightly increased in acid-contaminated soil. At the same dose of MC, single washing with higher MC concentration might be favorable to remove heavy metals, moreover, with much less wastewater generation.

Conclusions

The MC (the molar ratio of EDTA, GLDA, and citric acid was 1:1:3) may be a useful, environmentally friendly, and cost-effective chelators to remediate heavily multi-metal-contaminated soil.

     

Type of organic carbon amendment influences pH changes in acid sulfate soils in flooded and dry conditions

Purpose

Acid sulfate soils (ASS) are common in wetlands and can pose an environmental threat when they dry because oxidation of pyrite may cause strong acidification. Addition of organic matter can stimulate sulfate reduction during wet periods and minimize acidification during dry periods. However, the effect of the organic amendment may depend on its composition.

Materials and methods

Three wetland acid sulfate (sulfuric, hypersulfidic, and hyposulfidic) soils collected from different depth in one profile were used. The soils, unamended or amended with 10 g C kg^?1 as glucose, wheat straw, pea straw, or Phragmites litter, were incubated for 18 weeks under flooded conditions (“wet period”) followed by 10 weeks during which the soils were maintained at 100 % of maximum water-holding capacity (“dry period”).

Results and discussion

During the wet period, the pH decreased in the control and with glucose to pH 3–4, but increased or was maintained in residue-amended soils (pH at the end of the wet period about 7). In the dry period, the pH of the control and glucose-amended soils remained low, whereas the pH in residue-amended soils decreased. However, at end of the dry period, the pH was higher in residue-amended soils than in the control or glucose-amended soils, particularly with pea straw (C/N 50).

Conclusions

Amendment of acid sulfate soils with plant residues (particularly those with low to moderate C/N ratio) can stimulate pH increase during flooding and reduce acidification under oxidizing conditions.