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1.

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.
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2.

Purpose

Understanding the spatial distribution and sources of soil heavy metals (HMs) in a large city helps prevent and control soil pollution. This study aimed to investigate the spatial patterns of soil HMs and identify their main sources in a regional scale.

Materials and methods

A total of 110 topsoil samples were collected from Tai’an City, China. Cd, Cr, Cu, Hg, Ni, Pb, and Zn concentrations in each soil sample were determined. Geostatistics, geographic information system (GIS), and positive matrix factorization (PMF) were used to explore the spatial distribution of seven soil HMs and to reveal the main sources of soil HMs in Tai’an City, respectively.

Results and discussion

Soil Cd, Cr, Pb, and Zn generally showed slight pollution levels in the study area. However, soil Hg and Cu contents reached moderate to heavy pollution levels in some areas. Soil Hg content increased from north to south across the city, and the highest Hg concentration was detected in Ningyang County. Soil Cd, Cu, and Zn distributions exhibited a similar pattern, and their contents increased from west to east; the highest Cd, Cu, and Zn concentrations were found in Xintai County. The highest soil Ni concentration was obtained in the northeast of Feicheng and Xintai counties. PMF analysis revealed the following four potential sources of agricultural soil HMs in Tai’an City: industrial and mining activities, agricultural activities, residential living activities, and business activities. Soil Hg mainly originated from residential living activities, which accounted for 75.3% of the total source. The main sources of soil Ni were residential living activities, agricultural activities, and industrial and mining activities, which account for 38.2, 27.50, and 25.1% of the total source, respectively. Soil Cu was mainly produced by agricultural activities (36.6%), followed by residential living activities (29.8%) and industrial and mining activities (25.8%).

Conclusions

PMF combined with GIS could be effectively applied to determine the main sources of HMs in agricultural soils in a regional scale.
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3.

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.
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4.

Purpose

Extensive deposition of Pb, As, and Cs in soils may damage ecosystems and human’s health. Soil washing is the most conventional remediation method, and its efficiency depends on metal solubility in soil. This study aims to optimize operating variables of electro-kinetic field (EKF)-enhanced soil washing procedures.

Materials and methods

Soil samples from a Mississippi River Delta rice field were homogeneously spiked with Pb, As, and Cs, and contaminated soil was aged for 3 months. The remediation involved a first stage electro-kinetic process, followed by a soil washing procedure. Soil pH changes under EKF were studied. Effects of citric acid and reversed EKF were investigated for alleviating possible alkaline precipitation. In the washing procedure, soil washing time and cycles with different extractants were examined. The overall EKF-enhanced soil washing efficiencies were discussed as well.

Results and discussion

The implement of EKF offered an acidic soil environment around the anode areas for solubilizing metal(loid)s. Combined with EKF, citric acid was more conductive to desorb metal(loid)s. In addition, the reversed EKF effectively alleviated metal(loid) precipitation caused by alkalization in the first stage cathode areas. The EKF significantly enhanced metal(loid) extractions in the anode area of soils using Na2EDTA, CaCl2, and citric acid at pH of 2. The most preferable removal of Pb (80–98 %), As (48–63 %), and Cs (10–13 %) was achieved with three extractants. CaCl2 and citric acid were proved to be suitable alternatives to Na2EDTA for Pb extraction. A washing process of 2 h extraction with double washing cycles was optimized.

Conclusions

Soil washing time and cycles were major factors governing the metal(loid) removal from soil. Washing process of 2 h extraction with double cycles was optimized for further extraction based on higher washing efficiency. The EKF effectively improved washing efficiency while some electrical parameters need further studies for cost performance consideration.
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5.

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.
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6.

Purpose

The objective of this work was to identify hyperaccumulator plants and evaluate their capacity on copper mine tailings in the Antofagasta Region (Chile), considered one of the most arid in the world.

Materials and methods

Two native plant species, Gazania rigens and Pelargonium hortorum, were grown during 11 weeks on mine tailings. The physico-chemical characterization of the mine tailings under study indicated that the substrate required conditioning to support a phytoremediation system. In this respect, organic and inorganic amendments and mycorrizhal fungi were added to the substrate. Three treatments were designed to assess the effects of the amendments through an analysis of variance.

Results and discussion

Indicators of plant growth and development were measured weekly, and concentrations of Cd, Cu, Fe, Mn, Pb, Al, and Zn in roots of tailing-grown plants and substrate were measured at the end of the experiment.

Conclusions

The results were used to determine the bioconcentration factor (BCF), which demonstrated that both species act as excluders of Fe, Mn, Pb, Al, and Zn. In addition, it was found that both species present characteristics of potential accumulators of Cu.
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7.

Purpose

Soil contamination with heavy metals, such as Cd and Pb, has caused severe health and environmental risks all over the world. Possible eco-friendly solutions for Cd and Pb immobilization were required to reduce its mobility through various cost-effective amendments.

Materials and methods

A laboratory incubation study was conducted to assess the efficiency of biochar (BC), zeolite (ZE), and rock phosphate (RP) as passivators for the stabilization of Cd and Pb in paddy soil as well as soil microbial biomass. Various extraction techniques were carried out: a sequential extraction procedure, the European Community Bureau of Reference (BCR), toxicity characteristic leaching procedure (TCLP) test, and single extraction with CaCl2. The impact of passivators on soil pH, dissolved organic carbon (DOC), and microbial biomass (carbon, nitrogen, and phosphorus) was examined in the metal contaminated soil.

Results and discussion

The results showed that the exchangeable portion of Cd in soil was significantly reduced by 34.8, 21.6, and 18.8% with ZE, RP, and BC at a 3% application rate, respectively. A similar tendency of reduction in Pb soluble portion was observed by ZE (9.6%), RP (20%), and BC (21.4%) at a 3% application rate. Moreover, the TCLP leachate of Cd and Pb was apparently reduced by 17 and 30.3% with BC at a 3% application dose, respectively, when compared to the control. Soil pH, nutrients, and microbial biomass C, N, and P were significantly increased with the addition of BC, RP, and ZE passivators.

Conclusions

The results showed that the incorporation of BC, ZE, and RP significantly reduced the Cd and Pb mobility in paddy soil as well as enhanced soil nutrients and microbial biomass. Overall, among all the amendments, rice straw derived-BC performed better for Cd and Pb immobilization in paddy soil.
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8.

Purpose

The aim of this study was to quantify the effect of enhanced agronomic practices on cadmium (Cd) accumulation in the high-biomass energy plant Napier grass (Pennisetum purpureum Schumach).

Materials and methods

Potted-plant experiments were performed to investigate the effects of ammonium fertilizers and chelating agents, alone or in combination, on the growth, accumulation of Cd, and phytoextraction efficiency of P. purpureum on Cd-contaminated soil. The fertilizers included ammonium nitrate, ammonium sulfate, and ammonium chloride. The chelating agents included ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).

Results and discussion

The addition of ammonium fertilizers and chelating agents generally stimulated growth of P. purpureum, and the shoots accounted for 90.1–94.1% of the total biomass. The concentrations of Cd in different parts of P. purpureum plants were in the order root > leaf > stem. Ammonium chloride alone showed effectiveness in increasing root and shoot Cd concentrations compared to other amendments alone. Both EDTA alone and NTA alone significantly decreased root Cd concentration and increased shoot Cd concentration, while EDTA alone was more efficient on shoot and total Cd accumulation than that by NTA alone. The total accumulation of Cd in P. purpureum ranged from 1.10 to 2.05 mg per plant with 47.3–73.5% of Cd accumulation concentrated in shoots. The results indicate that P. purpureum can remove more Cd through phytoextraction than that by other hyperaccumulators.

Conclusions

Ammonium chloride led to the highest total Cd accumulation. Ammonium chloride applied alone or in combination with either EDTA or NTA resulted in the most effective agronomic approaches for P. purpureum phytoextraction of soil Cd.
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9.

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.
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10.

Purpose

This study aimed to reveal the temporal and spatial variation of soil heavy metal concentrations in the Three Gorges Reservoir area (TGR) water-level-fluctuating zone (WLFZ) and evaluated its pollution status and potential ecological risks and provide scientific basis for ecological risk prevention and ecological restoration of the TGR.

Materials and methods

This study was based on long-term monitoring of soil heavy metals (Cu, Pb, Cd, and Cr) before water level fluctuation (2008) and after 1 (2009), 4 (2012), or 7 (2015) cycles of water level fluctuation at the altitude of 155–172 m in the Wushan (WS) and Zigui (ZG) sections of the TGR, and pollution status and potential ecological risks of each heavy metal element were evaluated by index of geoaccumulation and potential ecological risk index.

Results and discussion

The Cd concentration increased with the increase in the number of reservoir water level fluctuations, whereas the concentrations of Cu, Cr, and Pb varied with the monitoring site. The Cd showed clear horizontal transfer characteristics. Moreover, with the increase of the frequency of water level fluctuations the Cd concentration at ZG (near the dam) were higher than those at WS (away from the dam). After 7 cycles of water level fluctuation, the concentrations of most soil heavy metal were not obvious differences between soil layers (except Pb). Before and after the reservoir water level fluctuation, Cd contamination level changed from pollution-free to strong or extremely polluted, Cu contamination level changed from pollution-free to moderately polluted, and Cr and Pb were pollution-free. Before the fluctuation of the reservoir water level, the potential ecological risk of Cd in the WS reached a classification of strongly polluted, whereas pollution at ZG was considered to be low level. However, after 4 cycles of water level fluctuation the Cd pollution level increased to a very high level, whereas Cu, Cr, and Pb remained consistently low.

Conclusions

There is an obvious temporal and spatial variation of heavy metal concentrations for WLFZ of TGR. Cd concentration increased with the increase in the number of reservoir water level fluctuations. Heavy metal concentrations changed from WS > ZG to WS < ZG after the impact of water level fluctuations. After 7 cycles of water level fluctuation, the distribution of heavy metals in different soil layers tends to be uniform (except Pb). Cd pollution is more serious, and there is a strong potential ecological risk.
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11.

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.
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12.

Purpose

The subject of this study is the sediment and wild lotus plants in unmanaged ponds, near Yichang City, contaminated by heavy metals. The objective is to determine the extent and frequency of heavy metal accumulation by lotus root in the ponds of rural areas and its significance to food safety and human health.

Materials and methods

The study area is located in the middle reaches of Yangtze River. The 11 sampling sites selected (Z1–Z11) were unmanaged ponds, and the lotus root samples were from wild plants. The lotus root and soil samples were processed using wet digestion, according to the national standard method; we tested concentration of heavy metal (Pb, Cd, Cr, As, Cu, and Zn). Both a single-factor index and an integrated pollution index were used to assess the heavy metal pollution of soil and wild lotus root. Correlation was used to examine the relationship of lotus root concentration to sediment concentration for each heavy metal.

Results and discussion

Cadmium (Cd) and arsenic (As) in both soil and pond sediment exceeded standards. The maximum single pollution index (SPI) for Cd and As was 1.16 and 1.15, respectively. The maximum integrated pollution index (IPI) for heavy metals was 2.17 for soil and 2.10 for sediment (moderate pollution). The heavy metal content in some samples of lotus root exceeded the national food standard and pose a health risk. The significant correlations of heavy metal concentrations (Pb, Cd, and As) in pond sediment with those in the surrounding soil show that the ponds act as sinks for agricultural nonpoint source pollution (NPS). The heavy metal concentrations in the peel of the edible tuber were 1.3~9.0 times higher than those in the inner flesh.

Conclusions

While Cd, Pb, and As concentrations in the sediment did not violate soil standards, concentrations in the lotus root did violate food standards. This species could be proposed as a suitable heavy metal bioindicator for the early stages of pollution from agricultural NPS.
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13.

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.
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14.

Purpose

Geochemical and mineralogical studies of soils potentially polluted by trace elements are basic to find the source of pollution, to understand the behavior of the contaminants in the environment, and to propose remediation and reclamation actions. This work reviews the role of the Mineralogy and Geochemistry to assess the hazard of soil contamination by trace elements in mining areas, focusing on three different case studies carried out in the Andalusian community (South Spain), with a Mediterranean temperate climate.

Materials and methods

Two significant mining districts were selected for this work: the Linares-La Carolina (Pb-Zn ores) and the Riotinto (Iberian Pyrite Belt, IPB) mining areas. Another case study was the Guadiamar basin, which soil was polluted by the spill produced in 1998 by the breakage of a mine tailing impoundment in Aznalcóllar mines (IPB). Soils, mine waste, and secondary precipitates were studied to approach the source of the pollution and the fate of the contaminants. Chemical composition (major and trace elements), soil parameters, and mineralogy of all materials selected were studied. In addition, the bioavailability of trace elements was determined by different methods.

Results and discussion

Pyrite and secondary phases are the main sources of pollution in the Riotinto area. Their stability is a key factor in the release of trace elements. The availability of trace elements in soils was lower in unpolluted leptosols than in contaminated orchards. In Linares-La Carolina, a severe pollution by Pb and a high availability (10–70% extracted with EDTA) were found. In Guadiamar basin, the residual pyrite sludge continues releasing trace elements to soil. Cd and Zn were mobile at pH <?6 and As at pH >?8, and Pb was quite immobile. Cd, Zn, and Pb can be coprecipitated by carbonates while As is mainly adsorbed by clays and iron oxyhydroxides.

Conclusions

The geochemical studies of soils polluted by mining activities allow to evaluate the availability of trace elements and their retention in soils. Therefore, geochemical and mineralogical studies are necessary for the assessment of soil pollution and remediation actions.
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15.

Purpose

Phytostabilization with native plant species might represent an economically more realistic and cost-effective option than excavation, soil washing, and sludge disposal for rehabilitation of degraded and polluted industrial areas. This work was done to assess the changes induced by native plant revegetation in the chemical properties and mobility-bioavailability of Pb and Zn pollutants of soil and post-washing sludges from an Italian brownfield site of national interest.

Materials and methods

A 5-year native plant revegetation of polluted soil and relative post-washing sludges from a steel plant was achieved in situ and ex situ in pot and in the presence and absence of peat as organic amendment. During the experiment, the vegetation growth was monitored (Adamo et al. In Int J Environ Sci Technol 12(6):1811–1824, 2015). Before and after plant growth, the substrates were studied for pH, organic carbon, and carbonate contents. Lead, Zn, and other metal mobility and leachability were investigated by water extraction. The metal bioavailability was estimated by diethylenetriaminepentaacetic acid (DTPA) extraction at pH 7.3. Sequential extractions (BCR procedure) were used to fractionate Pb and Zn in soil main geochemical forms. Plant ability to uptake metals was evaluated on the three most representative species: Bituminaria bituminosa, Daucus carota, and Dactylis glomerata.

Results and discussion

After 5 years of revegetation with native plants, the substrate pH and organic carbon content were respectively decreased and increased by plant growth, with changes masked by peat treatments. Although metal pollutants in both substrates were characterized by low water solubility and DTPA availability, after plant growth, an increase of rhizospheric Zn, Cu, Fe, and Mn solubility in H2O was detected. According to metal speciation, Pb and Zn were largely occluded in easily reducible manganese/iron oxides and trapped in the mineral structure of silicates, with no visible changes of distribution after plants. Water extraction always underestimated plant uptake, whereas DTPA and sequential extractions better predicted Pb and Zn uptake.

Conclusions

Despite the original extremely low mobility and bioavailability of metal pollutants in both soil and post-washing sludges, the acidification and increase of organic carbon content induced by peat amendments and plant growth enhance the solubility in water of metal-containing compounds. Therefore, attention must be paid to these effects in the long period. A continuous monitoring of the changes of pollutant mobility-bioavailability induced by native plant revegetation of brownfields is crucial to prevent risks to the surrounding environment and human health.
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16.

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.
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17.

Purpose

This work analyzes polychlorinated biphenyl (PCB) and heavy metal contamination in fluvial sediments and soils in an urban catchment, according to the geo-accumulation index and to soil and sediment quality guidelines. The catchment is located in Coimbra, Portugal, being affected by frequent flooding, and its main stream is a tributary to one of the major rivers in Portugal (Mondego). Given the presence of industrial activities over time, some inputs of pollutants are expected, but so far, the legacy of historic pollution in this catchment has not yet been investigated.

Materials and methods

Twenty-five samples were collected from nine sampling sites at the depths of 0–20, 20–40 and 40–60 cm (to provide a historic perspective) along longitudinal profiles (streamlines) and in soils downstream of pollution sources. These samples were analyzed for six heavy metals (Cu, Cr, Pb, Cd, Zn, Ni), organic carbon, pH and ten PCBs (IUPAC numbers 28, 30, 52, 101, 138, 153, 166, 180, 204, 209).

Results and discussion

Total PCB concentrations ranged 0.47–5.3 ng g?1 dry weight (dw), and levels increase from the bottom to the top layers, suggesting an increased input over the last 100 years. PCB congener distribution shows the dominance of hexachlorobiphenyls, especially PCB138, suggesting the existence of local sources. PCB levels did not exceed sediment quality levels, placing sediments/soil under class 1 (not contaminated) or class 2 (trace contamination) with respect to PCB. All six metals exceeded the lowest effect level for sediment quality criteria, and three (Cd, Pb and Zn) largely exceeded the clean levels for dredged materials, placing sediments in class 5 (heavily contaminated). Sampling site S1 presented the highest concentrations of Zn, Pb and Cd, and historic vehicle traffic was identified as the most likely source, given the vertical and horizontal profiles.

Conclusions

High levels of Pb, Cd and Zn were found in fluvial sediments at some locations of the Loreto catchment, likely from historic traffic sources. This urban area is frequently affected by flooding events and is currently being subject to urban redevelopment. During these events/actions, historic pollutants in the sediments might surface and be redistributed, impacting the downstream ecosystem of the major Mondego River or increasing the risk of exposure of the urban population.
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18.

Purpose

Studying the rate of chelant degradation is important to select environmental friendly compounds to assist phytoextraction. The objective of the present study was to evaluate degradation rate of complexes formed between synthetic or organic chelants and Pb aiming to increase the efficiency of phytoextraction while reducing adverse effects resulting from the Pb leaching.

Materials and methods

The following six chelating agents were tested: citric acid P.A., commercial citric acid, glutamic acid P.A., monosodium glutamate, nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA), besides a control treatment (no addition of chelating agent); they were applied at a concentration of 10 mmol dm?3 in pots containing 1 dm3 of Pb-contaminated soil.

Results and discussion

The results of this study showed that commercial citric acid adequately solubilized Pb to levels suitable for plant uptake and showed relatively rapid biodegradation in soil. Therefore, this commercial product may be a highly promising alternative for phytoextraction studies in the field. EDTA and NTA demonstrated high Pb solubilization ability but degraded comparatively slowly; therefore, they are not recommended for use in phytoextraction due to environmental risks regarding metal leaching.

Conclusions

The results of this study showed that commercial citric acid adequately solubilized Pb to levels suitable for plant uptake and showed relatively rapid biodegradation in soil, which is associated with a low risk of groundwater contamination. Therefore, this environmental friendly and low-cost product may be a highly promising alternative for inducing Pb phytoextraction.
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19.

Purpose

The aim of this work was to assess the concentrations of potentially toxic elements and to evaluate the soil quality of a typical Prosecco Denomination of Controlled and Guaranteed Origin vineyard of the Veneto region, NE Italy.

Materials and methods

Soil samples and leaves of Taraxacum officinale and Vitis vinifera were collected during spring–summer 2014. Element determination (Al, Cd, Cr, Cu, Fe, Mg, Mn, Ni, P, Pb, V, and Zn) were performed with ICP-OES after microwave digestion of samples. Soil quality was assessed via the biological soil quality (BSQ-ar) index. Lipid peroxidation test was performed to evaluate the vegetation oxidative stress, based on malondialdehyde (MDA) content via spectrophotometer.

Results and discussion

High concentrations of Al, Mg, and P were identified in soil, while high contents of Al, Cu, Fe, and Zn were found in V. vinifera leaves. The high concentrations in soil are probably due to agricultural activities, whereas those in leaves are probably due to atmospheric deposition and repeated use of foliar sprays in viticulture. The bioconcentration factor showed an effective transport of Cu, P, and Zn, from soil to leaf. The BSQ-ar values registered were similar to those obtained in preserved soils; hence, the biological class (VI) of these soils is high. The MDA content in T. officinale and V. vinifera leaves was below the reference value for T. officinale (2.9?±?0.2 μM), suggesting that the metal content did not stress the vegetation in the investigated site.

Conclusions

The MDA value for V. vinifera (1.1?±?0.7 μM) could be adopted as another control value for soil quality, which in our case is of “good quality.” Moreover, our results suggest that high concentrations of elements detected in the analyzed samples do not influence negatively the quality of soil, but a better agronomic management could improve soil quality in the studied area.
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20.

Purpose

The in situ stabilization of multielement-contaminated agricultural soils has limited effectiveness when using common single amendments. This study examined the use of drinking water treatment residues (WTR), based on (hydr)oxides of Fe, Al, or Mn, as a cost-effective solution to optimize the immobilization of metals (Cd, Pb, Zn) and As.

Materials and methods

Trace elements (TE) bioavailability was assessed under semi-controlled conditions in a pot study cultivating winter wheat (Triticum aestivum L. cv. Tiger) until maturity. An Fe-based WTR and a Mn-based WTR, applied at rates of 0.5 and 1% (m/m), were related to effects of lime marl (LM) application. Additionally, a bioassay with earthworms (Dendrobaena veneta) was conducted. Both bioassays were compared with measurements of NH4NO3-soluble, diffusive gradients in thin film (DGT)-available and soil solution TE concentrations, representing well-established surrogates for mimicking the bioavailable element fractions in soil.

Results and discussion

The application of the Fe-based WTR reduced As accumulation in vegetative wheat tissues (by up to 75%) and earthworms (by up to 41%), which corresponded with the findings from soil chemical analyses and improved plant growth and earthworm body weight. However, As concentrations in cereal grains were not affected, Cd or Pb accumulation by wheat was not mitigated, and Zn uptake was enhanced. By contrast, the Mn-based WTR effected the greatest reduction in Pb uptake, and lowered Cd transfer to wheat grain (by up to 25%). Neither the NH4NO3-soluble nor DGT-available concentrations matched with Cd and Zn accumulation in plants or earthworms, indicating interferences due to competition for binding sites according to the biotic ligand model.

Conclusions

The results obtained in this study suggest that a bioassay with key species prior to field application should be mandatory when designing in situ stabilization options. The application of WTR to an agricultural soil strongly affected TE bioavailability to plants and earthworms. Low application rates tended to improve biomass production of biota. Higher application rates involved risks (e.g., P fixation, TE inputs), and none of the amendments tested could immobilize all targeted elements.
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