Linking Ni and Cr concentrations to soil mineralogy: does it help to assess metal contamination when the natural background is high?

Purpose

In soils from serpentinitic areas the natural background of Ni and Cr is so high that the assessment of contamination by comparing metal concentrations with some fixed thresholds may give unreliable results. We therefore sought a quantitative relation between serpentines and Ni and Cr concentrations in uncontaminated soils, evaluated if the approach may help in establishing a baseline, and discussed if additional anthropogenic inputs of Ni and Cr can be realistically individuated in these areas.

Materials and methods

We analysed the total, acid-extractable and exchangeable concentrations of Ni and the total and acid-extractable concentrations of Cr in 66 soil horizons, belonging to 19 poorly developed and uncontaminated Alpine soils. The soils had different amounts of serpentines, depending on the abundance of these minerals in the parent material. We calculated an index of abundance of serpentines in the clay fraction by XRD and related total metal contents to the mineralogical index. We then tested the regressions on potentially contaminated soils, developed on the alluvial plain of the same watershed.

Results and discussion

We found extremely high total concentrations of Ni (up to 1,887 mg kg^–1) and Cr (up to 2,218 mg kg^–1) in the uncontaminated soils, but only a small proportion was extractable. Total Ni and Cr contents were significantly related to serpentine abundance (r ²?=?0.86 and 0.74, respectively). The regressions indicated that even small amounts of serpentines induced metal contents above 200 mg kg^–1, and the 95% confidence limits were 75 and 111 mg kg^–1 of Ni and Cr, respectively. When the regressions were tested on the potentially contaminated soils, a good estimate was obtained for Cr, while the Ni concentration was overestimated, probably because of some leaching of this element.

Conclusions

The concentrations of Ni and Cr that can be expected in soils because of the presence of small amounts of serpentines are comparable to the amounts accumulated in the soil because of diffuse contamination and potentially contaminated soils had metal concentrations falling in the range expected from the presence of natural sources. Only in the case of very severe contamination events, the identification of anthropogenic sources adding to the natural background would be feasible.     

Anthropogenic environmental impact in the Mediterranean coastal area of Koper/Capodistria,Slovenia

Purpose

Heavy metal content in soils could be a consequence of geogenic and different anthropogenic sources. In ancient times, soils in the Mediterranean region were affected by agriculture and viticulture, whereas more recently, industry and traffic might contribute more to their pollution. The aim of the study is to determine the extent of multisource heavy metal pollution in soils within the Koper area.

Materials and methods

Along the northern Adriatic Sea coast, around the port city of Koper/Capodistria, 24 topsoil samples were collected; sets of six samples representing four possible pollution sources: intensive agriculture, viticulture, port activities and industry. The parent material of the soil is mainly derived from the Eocene flysch weathered marls and calcarenites and the soil types are eutric. The chemical composition of the samples was determined by ICP-ES for oxides and several minor elements and by ICP-MS for heavy metals. The mineral composition of the selected samples was checked using X-ray powder diffraction. Different statistical analyses were performed on the normally distributed data.

Results and discussion

The mean concentrations of all samples are: Cr 215 mg kg^?1, Ni 81 mg kg^?1, Zn 67 mg kg^?1, Cu 44 mg kg^?1 and Pb and Co 18 mg kg^?1. The ANOVA showed significant differences only in CaO, C/TOT, P₂O₅, Co and Pb between those locations within reach of the different contamination sources. The observed average values of heavy metals are well below Slovenia’s Directive limit for Cu, Pb and Zn, close to but not above it for Co and above the action value for Cr and Ni. According to Igeo, soils from all the sampling locations are uncontaminated with Co, Ni and Pb, and uncontaminated to moderately contaminated with Cu and Zn at one port location, and with Cr at all locations.

Conclusions

The very high Cr and Ni levels could still be geogenic because soils developed on Eocene flysch rocks are enriched in both metals. Cr and Ni are not correlated because of their different levels of sorption and retention in carbonate soils. Cr was retained and concentrated in the sand fraction but Ni has been mobilised in solution. The only serious threat to the environment seems to be an illegal waste dumping area near the port.     

Remediation of an electroplating contaminated soil by EDTA flushing: chromium release and soil dissolution

Purpose

Remediation of soils contaminated with Cr (as Cr(III) complexes/precipitates and/or Cr(VI) oxyanion) and cationic metals (Cu, Ni, Zn, and Pb) by ethylenediaminetetraacetate (EDTA) flushing has been challenging and rarely investigated. This study aimed to evaluate the efficiency of EDTA flushing for metal extraction of soil from an electroplating site, with a specific focus on chromium release and soil dissolution.

Materials and methods

Column flushing tests were performed on a sandy soil contaminated by electroplating activities in the field. Three EDTA concentrations (5, 10, and 20 mM) and flow interruptions were employed to investigate the operation of EDTA flushing.

Results and discussion

Results demonstrated that Cr, Cu, and Ni were continuously released along with dissolution of Fe, Al, Mg, and Mn throughout the entire flushing process (up to 600 pore volumes), whereas Zn and Pb removal primarily occurred in the first 50–200 pore volumes. By comparing the Cr and Fe release patterns, the observed Cr release by EDTA flushing possibly resulted from a combination of dissolution of Fe oxides, dissolution of metal–chromate precipitates, and ligand competition for the surface sites (substitution reaction). The latter two mechanisms appeared to be more influential at the early stage. It was also revealed that soil dissolution was predominant, and metal extraction became inefficient at the later stage of flushing, especially with the concentrated EDTA solution. On the other hand, when the flushing process was temporarily paused (i.e., flow interruptions), Cr, Cu, Ni, and Zn concentrations elevated, whereas Pb levels in the effluent decreased, indicating the significance of rate-limited metal exchange of newly formed metal–EDTA complexes.

Conclusions

In consideration of EDTA utilization efficiency and potential ecological risks, diluted EDTA solution is recommended for field applications.     

Contents and chemical forms of heavy metals in school and roadside topsoils and road-surface dust of Beijing

Purpose

The concentration of human activities in urban systems generally leads to urban environmental contamination. Beijing is one of ancient and biggest cities on the world. However, information is limited on Beijing’s soil contamination, especially for roadside and campus soils. Thus, the aims of this study were to investigate the contents and chemical forms of toxic heavy metals Cd, Cr, Cu, Ni, Pb, and Zn in the road-surface dust, roadside soils, and school campus soils of Beijing. In addition, enrichment and spatial variation of these toxic heavy metals in the soils and dust were assessed.

Materials and methods

Topsoil samples were collected from the schools and roadside adjacent to main ring roads, and dust samples were collected from the surface of the main ring roads of Beijing. These samples were analyzed for total contents and chemical forms of Cd, Cr, Cu, Ni, Pb, Sc, Zn, Al, and Fe. Enrichment factors (EFs, relative to the background content) were calculated to evaluate the effect of human activities on the toxic heavy metals in soils.

Results and discussion

Heavy metal contents in the road dust ranged from 0.16 to 0.80, 52.2 to 180.7, 18.4 to 182.8, 11.9 to 47.4, 23.0 to 268.3, and 85.7 to 980.9 mg kg^?1 for Cd, Cr, Cu, Ni, Pb, and Zn, respectively. In the roadside soil and school soil, Cd, Cr, Cu, Ni, Pb, and Zn contents ranged from 0.13 to 0.42, 46.1 to 82.4, 22.7 to 71.6, 20.7 to 29.2, 23.2 to 180.7, and 64.5 to 217.3 mg kg^?1, respectively. The average EF values of these metals were significantly higher in the dust than in the soils. In addition, the average EF values of Cd, Cu, Pb, and Zn in the soils near second ring road were significantly higher than those near third, fourth, and fifth ring roads. Anthropogenic Cd, Pb, and Zn were mainly bound to the carbonates and soil organic matter, while anthropogenic Cu was mainly bound to oxides. The mobility and bioavailability of these metals in the urban soils of Beijing generally decreased in the following order: Cd?>?Zn?>?Pb?>?Cu?>?Ni?>?Cr; while in the dust, they decreased in the following order: Zn, Cu, and Cd?>?Pb?>?Ni?>?Cr.

Conclusions

Both EF and chemical forms documented that Cr and Ni in the soils and dust mainly originated from native sources, while Cd, Cu, Pb, and Zn partially originated from anthropogenic sources. In overall, Beijing’s road dust was significantly contaminated by Cd and Cu and moderately contaminated by Cr, Pb, and Zn, while Beijing’s roadside soil and school soil were moderately contaminated by Cd and Pb. However, the maximal hazard quotients (HQs) for individual Cd, Cr, Cu, Ni, Pb, and Zn and comprehensive hazard index (HI) of these metals in the dust and soil were less than 1, indicating that the heavy metals in the dust and soil generally do not pose potential health effects to children, sensitive population.     

Ecotoxic impact of suspended solids collected from polluted surface waters

Scope and background

Earlier studies showed that artificially contaminated particulate matter could be responsible for acute effects in water fleas and fish. Physical/chemical measurements on suspended solids and river water collected in the field showed that these samples were often contaminated with mixtures of toxic molecules.

Objectives

The present pilot study was started to investigate the possible ecotoxic impact of suspended solids collected in situ.

Methods

Suspended solids and river waters were collected from 22 locations of polluted rivers in the Flanders. An extensive list of chemical components and physical parameters were measured in these matrices. Partition coefficients for water column and suspended solids were calculated. Toxicity of suspensions of solid materials was investigated in 3 test organisms of different trophic levels: Bacteria (BIOMET®), filter feeder (Daphnia magna) and fish (rainbow trout (Oncor-hynchus mykiss) or zebrafish (Danio rerio)). The acute toxicity was measured in a worst-case scenario using high concentrations of solids resuspended in standard medium and at standard conditions.

Results and discussion

The partition coefficients were highly variable, showing that this parameter is not simply related to the octanol/water partition coefficient or to the total organic carbon content of the solids in field conditions, as is often assumed in exposure models. The field material of some locations was toxic. Bacteria were the most sensitive test organisms, showing EC20 values at field relevant concentrations. For some samples, acute toxic effects were seen in fish and water fleas. The chemical content of the samples was very complex and could not simply be related to toxicity. Some samples were highly contaminated with toxic chemicals and yet caused no toxic effects, while other samples did not show extremely high concentrations, but were toxic to the test organisms.

Conclusions

Results show that biotests are needed, next to chemical measurements, to estimate the toxic impact of complex environmental matrices. A better understanding of the adsorption/desorption behaviour of toxic molecules in the water compartment and in living organisms will contribute to a better environmental risk assessment.

Recommendations and outlook

The results indicate that the ecotoxic impact of suspended solids in the field should be further investigated in realistic (non-worst-case) conditions, i.e. for chronic effects at field relevant concentrations. And more extensive scientific research is needed to understand the adsorption/desorption behaviour of toxic molecules in different physicochemical matrices.     

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.     

Inorganic and organic pollution in agricultural soil from an emerging e-waste recycling town in Taizhou area, China

Purpose

The emerging recycling of electronic and electric waste (e-waste) is causing critical levels of soil pollution in those relatively poor towns surrounding the central cities, which have been involved in recycling activities for quite some time. Agricultural soil is of great importance due to its direct impact on food and human health. The objective of this study was to provide a systematic investigation of the contamination in agricultural soil for a range of inorganic compounds (Cr, Cd, Pb, Zn, Cu, and Ni) and organic compounds (PAHs and PCBs) in town A, an emerging e-waste recycling town in China.

Materials and methods

A total of 20 agricultural soil samples were collected from three sampling locations throughout town A. Levels of inorganic compounds (Cr, Cd, Pb, Zn, Cu, and Ni) and organic compounds (PAHs and PCBs) were determined by AAS, GC/MS, and GC/electron capture detector, respectively. Data was processed with SPSS 13 and Arcview 3.3 GIS software.

Results and discussion

The findings demonstrate that agricultural soil was contaminated to various extents by inorganic and/or organic pollutants. Comparison among the three sampling areas indicated that the soil was highly contaminated in the agricultural area near e-waste recycling workshops. Moreover, the contaminants (Cu, Pb, PAHs, and PCBs) may be connected through a common source as found in the Pearson correlations and cluster analysis.

Conclusions

There exists a heightened sense of awareness concerning the hazardous implications of current emerging e-waste recycling issues in the agricultural soil of those areas close to the central city in Taizhou.     

Heavy metal contamination of urban topsoils in a typical region of Loess Plateau,China

Purpose

Heavy metals pollution of city soil has become a serious environmental issue. Attention has been given to the issue of soil contamination in big cities, but little research has been done in the Loess Plateau, which is the largest loess deposition area in the world. The aim of this study was to assess the contamination of topsoil.

Materials and methods

Forty soil samples were collected from different districts and sieved through nylon sieves. The coarse particles (2 mm) were used to determine pH and electrical conductivity using a suspension of 1:5 soil to deionized water. The fine particles (150 μm) were used to determine soil organic matter and selected heavy metals. Metals were measured in digested solutions by a flame atomic absorption spectrophotometer.

Results and discussion

The mean concentrations of heavy metals in urban soils in the study area are significantly lower than the mean concentrations across China. The integrated pollution index was determined to be 1.13, indicating moderate pollution. Weathering of parent material, the use of pesticide and fertilizer, discharge of waste from traffic, wastes from commodities and industry, and coal combustion are considered to be the main sources of heavy metal pollution in the study area.

Conclusions

The results indicate that, at least in the study area, land use greatly influences the soil quality and heavy metal contents in urban topsoils. Soil backfill may change heavy metal contents to some extent. Deep digging and backfill can be effectively used for the remediation of heavy metal contaminated soil and sediments.     

Application of the Weng’s ratio for the identification of Zn, Cu, and Pb contamination in soils and sediments

Purpose

This work explores the application of the use of Zn, Cu, and Pb relative contents as a new type of normalization method for geochemical properties of soils and sediments in an Atlantic Basin (Anllóns River, NW Spain). The method is based on the conservative behavior of these elements, which exhibit a certain concentration ratio that remains stable as long as there are no human disturbances.

Materials and methods

The average relative contents of Zn, Cu, and Pb were calculated by dividing the concentration of each metal in soils or sediments, in the <63-μm fraction, by the sum of Zn, Cu, and Pb, expressed as a percentage. The evaluation of the sum of the average relative concentrations of Zn, Cu, and Pb (Ri), together with three standard deviations for each element, namely, Ri ± 3Si, allows a hexagon to be constructed, represented in ternary diagrams of Zn:Cu:Pb. Following the method proposed by Weng et al. (Environ Geol 45:79–85, 2003), those samples falling outside the hexagon must be considered outliers.

Results and discussion

Results obtained confimed the conservative behavior between the relative contents of Zn, Cu, and Pb in surficial samples (soils, bed, and suspended sediments). Only sediment cores displayed nonconservative behavior, showing a marked Pb enrichment, with respect to the surficial samples. When Zn, Cu, and Pb relative contents were plotted in ternary diagrams, outliers were best classified when the hexagon was drawn with standard deviations of samples from the study area. The hexagon drawn with an international database of soils and sediments showed a poorer classification of outliers.

Conclusions

The results showed that total Zn, Cu, and Pb relative contents may be employed to investigate anthropogenic disturbances of these elements in soils and sediments of the Anllóns River Basin, thus corroborating that this type of normalization may be employed as a tool to assess outliers in a contaminated area.     

Assessment of the stability of chromium in remedied soils by Pannonibacter phragmitetus BB and its risk to groundwater

Purpose

Acid rain can accelerate the acidification of the chromium-contaminated soils, resulting in chromium releasing into soil solution and causing ecological risk. The current study aims to investigate the release of chromium in the remedied soils by Pannonibacter phragmitetus BB under the simulated acid rain leaching and to assess its risk to groundwater.

Materials and methods

P. phragmitetus BB was utilized to remedy the Cr(VI)-contaminated soils at two levels (80 and 1,276 mg kg^?1) by the column leaching experiment, and the chemical remediation with ferrous sulfate was used as a control. The remedied soils by P. phragmitetus BB and ferrous sulfate were leached under the simulated acid rain to evaluate the release of chromium. Furthermore, the risk of chromium release from the remedied soils to the groundwater was assessed by a fuzzy comprehensive evaluation method.

Results and discussion

The average concentrations of water-soluble Cr(VI) in the remedied soils by P. phragmitetus BB were reduced to less than 5.0 mg kg^?1. Under leaching situation with the simulated acid rain, the release of total chromium and Cr(VI) from the remedied soils by P. phragmitetus BB and ferrous sulfate declined rapidly with the extended leaching time. However, the release amounts of total chromium and Cr(VI) from the remedied soil by P. phragmitetus BB more efficiently deceased as compared with that by ferrous sulfate remediation. Carbonate-bounded, exchangeable, and organics-bonded chromium were the major chromium-releasing sources under the simulated rain leaching. After microbial remediation with P. phragmitetus BB and chemical remediation with ferrous sulfate, the risk grades of the remedied soils to groundwater declined from classes 11 to 5 and 6, respectively.

Conclusions

The risks of the remedied soils by both microbial remediation with P. phragmitetus BB and chemical remediation with ferrous sulfate to groundwater effectively decreased and microbial remediation more significantly declined the chromium risk to groundwater than chemical remediation.     

Cadmium contamination of sediments in the water reservoirs in Silesian Upland (southern Poland)

Purpose

Cadmium (Cd) is considered a toxic element and its concentrations are relevant to human health and the environment. Therefore, the purpose of the study was to determine the extent to which the bottom sediments of water bodies (artificial lakes and ponds) in the Silesian Upland in southern Poland are contaminated with Cd; an attempt was also made to determine the factors that condition spatial differences in the concentration of this element between individual water bodies in the region.

Materials and methods

Measurements of the Cd content in bottom sediments were carried out in 35 water bodies in southern Poland in 2011 and 2012. Depending on the surface area and morphometric characteristics, from two to nine samples representative in terms of sediment thickness were collected in each water body. Cadmium concentrations were determined for 92 0.25 g aliquots using the TD-ICP method.

Results and discussion

Cadmium content in all samples (0.7–580.0 mg kg^?1) was higher than the natural range of concentrations for this element in the Earth’s crust (0.1–0.3 mg kg^?1) and the geochemical background for Poland (0.5 mg kg^?1) and, with a few exceptions, was also higher than the preindustrial concentration (1.0 mg kg^?1) and the regional geochemical background (2.5 mg kg^?1). Adopting natural Cd concentrations in the Earth’s crust (0.1–0.3 mg kg^?1) as the baseline for the geoaccumulation index (I_geo), the sediments examined can be classified as extremely and heavily contaminated (and moderately contaminated in a small number of cases). The assessment of sediment quality based on I_geo, with the regional geochemical background (2.5 mg kg^?1) adopted as the baseline, results in non-contaminated and moderately contaminated sediments being dominant with a far smaller number of heavily and extremely contaminated ones.

Conclusions

In the case of several water bodies, Cd concentrations were at record levels that have not been found anywhere else in the world. On the basis of the I_geo, sediments of varying quality were found—from virtually uncontaminated to extremely contaminated. The I_geo index as an indicator of the quality of bottom sediments is a measure that requires careful interpretation, especially when different concentration levels regarded as natural are used for determining its value.

     

Intracellular chromium accumulation by <Emphasis Type="Italic">Streptomyces</Emphasis> sp. MC1

Streptomyces sp. MC1, previously isolated from sugar cane, has shown ability to reduce Cr(VI) in liquid minimal medium and soil samples. The objective of this work was to demonstrate the intracellular chromium accumulation by Streptomyces sp. MC1 under different culture conditions. This strain was able to accumulate up to 3.54 mg of Cr(III) per gram of wet biomass, reducing the 98% of Cr(VI) and removing 13.9% of chromium from the culture medium supernatants. Streptomyces sp. MC1 chromium bioaccumulation ability was corroborated by using Timm’s reagent technique, a low-cost method, which has been used by first time to detect chromium deposits in bacteria. The results of atomic absorption spectrometry, scanning electron microscopy, and energy dispersive X-ray analysis suggest that the mechanism of Cr(VI) resistance observed in Streptomyces sp. MC1 includes adsorption coupled with reduction to Cr(III), and finally, Cr(III) bioaccumulation. This mechanism have special relevance to remediation of Cr(VI) contaminated environments by Streptomyces sp. MC1.     

Simultaneous removal of Cu and PAHs from dredged sediments using flotation

Purpose

This study addresses the feasibility of a flotation technique, using a lab-scale flotation cell, to simultaneously remove both metals and polyaromatic hydrocarbons (PAHs) from fine sediment fractions (<250 μm) that are potentially contaminated with copper (Cu).

Materials and methods

A multiple flotation process with three consecutive flotation stages was performed on three sediments (13S, 14B, and 24A) with different particle size distributions, Cu and PAH concentrations, and organic matter contents.

Results and discussion

Flotations performed under selected conditions allowed for significant removal of both Cu (61–70 %) and PAHs (75–83 %) with acceptable froth recoveries of approximately 23–29 %. Removal rates for arsenic, lead, and zinc were 48–61, 40–48, and 32–36 %, respectively. Flotation selectivity of Cu was greatly influenced by the contents of fine particles and organic matter of the sediments. The maximum flotation selectivity was obtained for the 53–125-μm size fraction. The high flotation selectivity of Cu (2.5–3.2) and PAHs (3.0–3.6) demonstrated the feasibility of flotation to treat soils or sediments containing both organic and inorganic pollutants.

Conclusions

Overall, the flotation results showed a high selectivity for both Cu and PAHs and demonstrated the feasibility of flotation to treat media contaminated with organic and inorganic contaminants.     

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.     

Occurrence of Cu and Cr in the sedimentary humic substances and pore water from a typical sugar cane cultivation area in São Paulo,Brazil

Purpose

The purpose of this paper is to study the interactions of sedimentary humic substances (SHS) from a sugarcane cultivation area with Cu(II) and Cr(III) and to evaluate the occurrence of these metals in the pore water and SHS.

Materials and methods

For this study, the northwestern region of the State of São Paulo, Brazil, which is considered the region with the highest production of sugar cane in the state, was selected. Samples of sediment were collected from four sampling sites in the Preto, Turvo, and Grande rivers. The SHS and pore water were extracted from the sediment using the method suggested by the International Humic Substances Society and centrifugation, respectively. The complexing capacity (CC) of the SHS for Cu(II) and Cr(III) was determined by individually titrating these metals with an ultrafiltration system using tangential flow. The total concentrations of Cr and Cu were determined for the pore water, sediments, and humic substances with graphite furnace atomic absorption spectrometry and Zeeman background correction after an acid digestion, according to the methods described in US EPA Method 3050B.

Results and discussion

The SHS from a site in the Turvo River, which is typically cultivated with sugarcane, possessed the highest concentration of Cu bound to SHS (25.0%), the largest CC (0.63 mmol Cu g^?1 HS) and the highest concentration of this metal in the pore water (1.38 mg Cu Kg^?1 sed.). For Cr, the SHS collected from a location on the Preto River dam had the largest CC (0.90 mmol Cr g^?1 HS) and the lowest Cr content in the pore water (0.29 mg Cr Kg^?1 sed.), indicating that there was an inverse relationship between the CC and the concentration of metal available in the pore water.

Conclusions

Sedimentary humic substances might be one of the regulatory factors controlling the availability of Cu and Cr in the sediments found in a typical region that has been planted with sugarcane. Distinct behaviors were observed between the two elements investigated; higher CC and a larger fraction of Cu(II) were found in the pore water of samples originating from sugarcane crops. The opposite behavior was observed for the Cr(III) species.     

Emerging resistant microbiota from an acidic soil exposed to toxicity of Cr, Cd and Pb is mainly influenced by the bioavailability of these metals

Purpose

The effect of pollutants in soil microorganisms is an important issue in order to understand their toxic effects in the environment, as well as for developing adequate bioremediation strategies. In this sense, the main objective of this study was to assess the involvement of the indigenous microbiota of an acidic forest Mediterranean soil by artificial pollution with heavy metals, and to detect and isolate resistant microorganisms that could be useful for bioremediation.

Materials and methods

Samples from a previously unpolluted acidic forest soil were amended with Cr(VI), Cd(II) or Pb(II) at total amounts ranging from 0.1 to 5,000 mg?kg^?1. These soil microcosms were incubated under controlled laboratory conditions for 28 days. Soluble fractions of metals were determined from aqueous extracts. Both activity and composition of the microbial community were assessed, respectively, by respirometric assays and molecular analysis (polymerase chain reaction denaturing gradient gel electrophoresis). The isolation of metal-resistant microorganisms was attempted by culture plating from microcosms incubated with high concentrations of metals. Isolated strains were tested in cultures with minimal medium to check for their metal resistance and their capacity to reduce the presence of toxic Cr(VI).

Results and discussion

A decrease in the soil respirometric activity and changes in the microbial community composition were detected from 10/100 mg?kg^?1 Cr and 1,000 mg?kg^?1 Cd and Pb. Presumably resistant bacterial and fungal populations developed in most of these polluted microcosms; however, the microbiota was severely impaired at the highest additions of Cr. Even though Cr was the most damaging metal in soil microcosms, if the soluble fractions of metals are considered instead of their total added amounts, the comparison among their toxic effects suggests a similar potential toxicity of Cr and Pb. Isolated multiresistant microorganisms were related mainly to Actinobacteria, Firmicutes and Ascomycota. Some of them showed the capacity to reduce Cr(VI) concentrations between 54 % and 70 % of the initial value. These strains were affiliated to several species of Streptomyces and Bacillus.

Conclusions

The combination of respirometric assays with molecular methods has been useful to assess the effect of metals on the soil microbial community, which can greatly be explained by their differential bioavailability. Cultivation-dependent and -independent approaches have proved the presence and development of multiresistant microorganisms in a previously unpolluted soil. Due to their properties, some of the isolated strains are potentially useful for soil bioremediation.     

Field validation of chlordecone soil sequestration by organic matter addition

Purpose

The use of chlordecone (CLD) has caused pollution of soils, which are now a source of contamination for crops and ecosystems. Because of its long-term impacts on human health, exposure to CLD is a public health concern and contamination of crops by CLD must be limited. To this end, we conducted field trials on chlordecone sequestration in soil with added compost.

Materials and methods

The impact of added compost on chlordecone sequestration was measured in nitisols. After characterization of the soil, the transfer of chlordecone from soil to water was assessed in a leaching experiment and from soil to two crop plants in a nitisol plot. Finally, to understand the underlying processes, changes in CLD content were measured in soil fractions and soil porous properties were assessed after the addition of compost.

Results and discussion

A rapid seven-fold decrease in water extractable CLD was observed in amended soils. Five percent amendment led to a significant reduction in the contamination of crops by CLD; edible radish tubers were 50% more contaminated without added compost and cucumber fruits were 60% more contaminated. After the addition of compost, CLD content increased in the fraction of pre-humified or partially mineralized organic debris. Finally, in contrast to andosols, adding compost to nitisols did not affect the soil microstructure.

Conclusions

Increasing chlordecone sequestration by adding compost could be an alternative solution until soil decontamination techniques become available. This could be a provisional way to control further release of CLD from contaminated soils towards other environmental compartments.     

Using in situ solid phase microextraction (SPME) for depth profiling in sediments treated with activated carbon

Purpose

Sediment contamination in US waterways is an expensive and complicated issue, and as acceptance of nontraditional sediment remediation strategies broadens, novel and efficient methods to assess and monitor the bioavailability of hydrophobic organic contaminants (HOCs) in contaminated sediments will play an important role.

Materials and methods

In this project, solid phase microextraction (SPME) fibers inside perforated steel tubes were used as in situ passive samplers to measure polycyclic aromatic hydrocarbon (PAH) concentrations in sediment before and after treatment with activated carbon (AC). Two modes of waterjet amendment injection were used to apply the AC. In the first treatment, a single 2-min injection was shot into the center of a test vessel, and in the second treatment, multiple 7-s injections in a grid were placed in sediment.

Results and discussion

In the single injection, no treatment was observed 5 cm away from the injection, while at 2.5 cm, >90 % decrease of PAH pore water concentration was observed, indicating a similar bioavailability decrease. In the multiple injection experiment, >90 % PAH pore water level reductions were observed throughout the test vessel. Highly contaminated and less contaminated sediments were mixed with 0–5 % AC by weight to develop AC treatment curves. Over 99 % reduction in PAH pore water concentrations and bioavailability was observed in the less contaminated sediment at 3 % AC, while 99 % reduction was never reached even at 5 % AC addition in the highly contaminated sediment. Different treatment curves were observed for the different contaminated sediments. In situ equilibration times were 120, 215, and 250 h for phenanthrene, pyrene, and benzo(a)anthracene, respectively.

Conclusions

The results show that in situ SPME is a viable method to observe AC treatment and evaluate reductions in pore water concentrations and bioavailability.     

An innovative stabilization/solidification treatment For contaminated soil remediation: demonstration project results

Background, aim, and scope

An innovative stabilization/solidification (S/S) process using high-performance additivated concrete technology was developed for remediating soil contaminated by metals from abandoned industrial sites. In order to verify the effectiveness of this new ex situ S/S procedure, an area highly contaminated by metallic pollutants (As, Cd, Hg, and Pb), due to the uncontrolled discharge of waste generated from artistic glass production on the island of Murano (Venice, Italy), was selected as a case study. The technique transforms the contaminated soil into an aggregate material suitable for reuse as on-site backfill. This paper reports the main results of the demonstration project performed in collaboration with the local environmental protection agency (ARPAV).

Materials and methods

An ex situ treatment for brownfield remediation, based on the transformation of contaminated soil into very dense, low porous, and mechanically resistant granular material, was set up and tested. Specific additives (water reducers and superplasticizers) to improve the stabilized material properties were developed and patented. A demonstration plant assembled on the study area to treat 6 m³ h^–1was then tested. After excavation, the contaminated soil was screened to remove coarse material. The fraction Ø?>?4 mm (coarse fraction), mainly composed of glass, brick, concrete, and stone debris, was directly reused on site after passing through a washing treatment section. The highly polluted fraction Ø?≤?4 mm (fine fraction) was treated in the S/S treatment division of the plant (European patent WO/2006/097272). The fine fraction was mixed with Portland cement and additives defined on the basis of the high performance concrete technique. the mixture was then granulated in a rolling-plate system. After 28 days curing in an onsite storage area to allow for cement hydration, the stabilized material was monitored before its in situ relocation. The chemical, mechanical, and ecotoxicological reliability and performance of the treatment was checked. Metal leachability was verified according to four leaching test methods: Italian Environmental Ministry Decree (1998), EN 12457 (2002) tout court, amended only with MgSO₄ and, lastly, with artificial sea water. The mechanical properties were measured according to BS (1990) and AASHTO (1999) to obtain the Aggregate Crushing Value and California Bearing Ratio, in that order. Moreover, leachate samples prepared with artificial seawater were assessed via the Crassostrea gigas embryotoxicity test and Vibrio fischeri bioluminescence inhibition test to discriminate the presence of potential ecotoxicological effects for the brackish and saltwater biota.

Results

Outcomes from all leachate samples highlighted the effectiveness of the remediation treatment, fully complying with the Italian legislation for non-hazardous material reuse under a physicochemical viewpoint. The stabilized granular material demonstrated high mechanical strength, low porosity, and leachability. Moreover, ecotoxicological surveys indicated the presence of low toxicity levels in leachate samples according to both toxicity tests.

Discussion

Remediated soil samples revealed a significant decrease in leachability of heavy metals as a consequence of the application of additivated cement that enhanced granular material properties, resulting in improved compactness due to the reduction in water content. The toxicity data confirmed this state-of-the-art technique, indicating that leachates could be deemed as minor acutely toxic.

Conclusions

The proposed S/S treatment proved to be able to remediate soil contaminated by heavy metals through trapping pollutants in pellet materials presenting adequate physicochemical, mechanical, and ecotoxicological properties in order to prevent leachability phenomena, their reclamation, and reuse being made easier by its granular form.

Recommendation and perspectives

This project foresees long-term monitoring activity over several years (until 2014) to consider treatment durability.     

Chromium (VI) Retrieval from Chromium Ore Processing Residues by Electrokinetic Treatment

Electrokinetics (EK) was investigated as a possible technique for in-situ treatment of leachable chromium at a built site contaminated with chromium ore processing residues (COPR). A preliminary EK experiment was carried out at the laboratory scale on an undisturbed COPR core sample. Methods applied for material and pore water characterization before and after EK treatment addressed physical aspects by laser diffraction granulometry, pycnometry and pore water content, mineralogical aspects by X-ray diffraction, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, and chemical aspects by inductively coupled plasma-atomic emission spectroscopy and atomic absorption spectroscopy for elemental composition, spectrophotometry for Cr(VI) analysis, and potentiometry for pH determination. EK was run at 1 V/cm with no external constraints on current intensity. The EK experiment reached an extraction of 72% of the total leachable Cr(VI) after only 10 days of treatment and 84% after 20 days. Material texture, composition, and pH remained similar. These results indicate that EK presents a potential solution for extracting leachable Cr(VI) from COPR sites. The impounded COPR material appeared to be heterogeneous in composition at all scales, from field to lab sample, adding to the challenge of in-situ treatment.