Contaminated Soil Profiles Research Articles

Microbial adaptation in vertical soil profiles contaminated by an antimony smelting plant

Antimony mining has resulted in considerable pollution to the soil environment. Although studies on antinomy contamination have been conducted, its effects on vertical soil profiles and depth-resolved microbial communities remain unknown. The current study selected three vertical soil profiles (0-2m) from the world's largest antimony mining area to characterize the depth-resolved soil microbiota and investigate the effects of mining contamination on microbial adaptation. Results demonstrated that contaminated soil profiles showed distinct depth-resolved effects when compared to uncontaminated soil profiles. As soil depth increased, the concentrations of antimony and arsenic gradually declined in the contaminated soil profiles. Acidobacteria, Chloroflexi, Proteobacteria and Thaumarchaeota were the most variable phyla from surface to deep soil. The co-occurrence networks were loosely connected in surface soil, but obviously recovered and were well-connected in deep soil. The metagenomic results indicated that microbial metabolic potential also changed with soil depth. Genes encoding C metabolism pathways were negatively correlated with antimony and arsenic concentrations. Abundances of arsenic-related genes were enriched by severe contamination, but reduced with soil depth. Overall, soil depth-resolved characteristics are often many meters deep and such effects affected the indigenous microbial communities, as well as their metabolic potential due to different contaminants along vertical depths.

Effects of biochar on cadmium (Cd) uptake in vegetables and its natural downward movement in saline-alkali soil

ABSTRACT The focus was to assess the effects of biochar on Cd uptake by various vegetables and its downward movement in saline-alkali soil and carried out in polluted pots experiment. The results showed that the biomass of vegetables increased significantly by 16.9% to 519.9% while the Cd concentration in green pepper and eggplant fruits was decreased by 6.8% to 11.5% and 15.1% to 15.4% with the biochar application. The Cd in contaminated soil profile was transferred from topsoil (0-6 cm) to subsoil (6-12 cm) that was observed as 14.30 ± 4.17 mg kg-1. The concentrations of Cd in soil with different fractions like exchangeable, reducible and oxidizable and the Cd uptake by vegetables were reduced. The release of residual Cd was decreased by 0.3 to 20.1% over time with biochar application (0-12 cm). The biochar was effective in mitigating the soil Cd pollution by preventing the vertical Cd leaching.

Tracing anthropogenic thallium in soil using stable isotope compositions.

Thallium stable isotope data are used in this study, for the first time, to apportion Tl contamination in soils. In the late 1970s, a cement plant near Lengerich, Germany, emitted cement kiln dust (CKD) with high Tl contents, due to cocombustion of Tl-enriched pyrite roasting waste. Locally contaminated soil profiles were obtained down to 1 m depth and the samples are in accord with a binary mixing relationship in a diagram of Tl isotope compositions (expressed as ε(205)Tl, the deviation of the (205)Tl/(203)Tl ratio of a sample from the NIST SRM 997 Tl isotope standard in parts per 10(4)) versus 1/[Tl]. The inferred mixing endmembers are the geogenic background, as defined by isotopically light soils at depth (ε(205)Tl ≈ -4), and the Tl emissions, which produce Tl-enriched topsoils with ε(205)Tl as high as ±0. The latter interpretation is supported by analyses of the CKD, which is also characterized by ε(205)Tl ≈ ± 0, and the same ε(205)Tl value was found for a pyrite from the deposit that produced the cocombusted pyrite roasting waste. Additional measurements for samples from a locality in China, with outcrops of Tl sulfide mineralization and associated high natural Tl backgrounds, reveal significant isotope fractionation between soils (ε(205)Tl ≈ +0.4) and locally grown green cabbage (ε(205)Tl between -2.5 and -5.4). This demonstrates that biological isotope fractionation cannot explain the isotopically heavy Tl in the Lengerich topsoils and the latter are therefore clearly due to anthropogenic Tl emissions from cement processing. Our results thus establish that isotopic data can reinforce receptor modeling for the toxic trace metal Tl.

Biogeochemical Fractions of Mercury in Soil Profiles of Two Different Floodplain Ecosystems in Germany

A special sequential extraction (SE) procedure for mercury (Hg) was conducted to determine biogeochemical fractions of Hg and their controlling factors in four contaminated soil profiles located in two distinct floodplain ecosystems which differ in their industrial histories and thus in their Hg loads. The first study area is located at the Wupper River (Western Germany) and the soil profiles reveal sum of Hg (Hgsum) concentrations up to 48 ppm. The second study area is located at the Saale River (Eastern Germany) and the soil profiles have Hgsum concentrations up to 4.3 ppm. The majority of Hg was found in fraction IV (FIV, Hg0) for both study areas, indicating its anthropogenic origin. Moreover, we have detected Hg in fraction V (FV) and in fraction III (FIII). As Hg in FV is mostly associated with Hg sulfides being formed under reducing conditions, it indicates reduction processes which usually occurred during flooding. Mercury in FIII (organo-chelated Hg) exhibits a moderate mobility and a high methylation potential. Between Hg in FIII and hot-water-extractable carbon (CHWE) as a measure of easy degradable, labile soil organic matter, we found a significant correlation. Sum of Hg seem to have a high affinity to organic carbon (Corg). The concentrations of Hg in the mobile and exchangeable fractions FI and FII were low. Moreover, the significant positive correlation between iron (Fe) and Hg in FIV indicate an interaction between Hg and Fe. The majority of the Hg in our soils is considered to be relatively immobile. However, since the formation of more mobile Hg species via oxidation or methylation might occur in floodplain soils, the low Hg concentrations in mobile fractions should not be underestimated due to their high mobility and potential plant availability.

Mobility of arsenic, cadmium and zinc in a multi-element contaminated soil profile assessed by in-situ soil pore water sampling, column leaching and sequential extraction

Three methods for predicting element mobility in soils have been applied to an iron-rich soil, contaminated with arsenic, cadmium and zinc. Soils were collected from 0 to 30 cm, 30 to 70 cm and 70 to 100 cm depths in the field and soil pore water was collected at different depths from an adjacent 100 cm deep trench. Sequential extraction and a column leaching test in the laboratory were compared to element concentrations in pore water sampled directly from the field. Arsenic showed low extractability, low leachability and occurred at low concentrations in pore water samples. Cadmium and zinc were more labile and present in higher concentrations in pore water, increasing with soil depth. Pore water sampling gave the best indication of short term element mobility when field conditions were taken into account, but further extraction and leaching procedures produced a fuller picture of element dynamics, revealing highly labile Cd deep in the soil profile.

Presence of Actinobacterial and Fungal Communities in Clean and Petroleum Hydrocarbon Contaminated Subsurface Soil

Relatively little is known about the microbial communities adapted to soil environments contaminated with aged complex hydrocarbon mixtures, especially in the subsurface soil layers. In this work we studied the microbial communities in two different soil profiles down to the depth of 7 m which originated from a 30-year-old site contaminated with petroleum hydrocarbons (PHCs) and from a clean site next to the contaminated site. The concentration of oxygen in the contaminated soil profile was strongly reduced in soil layers below 1 m depth but not in the clean soil profile. Total microbial biomass and community composition was analyzed by phospholipid fatty acid (PLFA) measurements. The diversity of fungi and actinobacteria was investigated more in detail by construction of rDNA-based clone libraries. The results revealed that there was a significant and diverse microbial community in subsoils at depth below 2 m, also in conditions where oxygen was limiting. The diversity of actinobacteria was different in the two soil profiles; the contaminated soil profile was dominated by Mycobacterium -related sequences whereas sequences from the clean soil samples were related to other, generally uncultured organisms, some of which may represent two new subclasses of actinobacteria. One dominating fungal sequence which matched with the ascomycotes Acremonium sp. and Paecilomyces sp. was identified both in clean and in contaminated soil profiles. Thus, although the relative amounts of fungi and actinobacteria in these microbial communities were highest in the upper soil layers, many representatives from these groups were found in hydrocarbon contaminated subsoils even under oxygen limited conditions.

Half-lives of self-purification for various isotopes in soils of the Chernobyl Exclusion Zone

During 2001-2002 we investigated current contamination of soils in several places in the Chornobyl zone. We have measured the content of alpha emitting isotopes Pu, 241 Am, 154,155 Eu, 90 Sr, and 137 Cs in layers of soil up to the depth of 30cm. By including the two mechanisms of migration: convection and diffusion in our model, we were able to estimate the ecological and effective half-lives of self-purification processes for these layers of soil. Effective half-lives vary from 20 to 400 years dependent upon the type of soil and the isotopes. Understanding the rates of migration and dissipation of radioisotopes in the environment is essential for predicting the effectiveness of natural remediation processes, or self-purification. The rate of radionuclide migration in the different soil types can differ markedly. As a result, the ecological half-life (T1/2,ecol) of self-purification processes for upper layers of soil may exceed, or be considerably shorter than, the physical half-life (T1/2) of the radionuclide. The effective half-life (T1/2,eff )i s a measure of self-purification and includes both ecological and physical losses in accordance with the formula: 1/T1/2,eff = 1/T1/2,ecol + 1/T1/2. We have evaluated the effective half-lives for Pu, 241 Am, 154,155 Eu, 90 Sr, and 137 Cs using measurements of contaminated soil profiles from research sites in the Red Forest and Glyboky Lake inside the Chornobyl Exclusion Zone.

Changes in arsenic speciation through a contaminated soil profile: A XAS based study

An impacted soil located near an industrial waste site in the Massif Central near Auzon, France, where arsenical pesticides were manufactured, has been studied in order to determine the speciation (chemical forms) of arsenic as a function of soil depth. Bulk As concentrations range from 8780 mg kg − 1 in the topsoil horizon to 150 mg kg − 1 at 60 cm depth. As ores (orpiment As 2S 3, realgar AsS, arsenopyrite FeAsS) and former Pb- and Al-arsenate pesticides have been identified by XRD at the site and are suspected to be the sources of As contamination for this soil. As speciation was found to vary with depth, based on XRD, SEM-EDS, EPMA measurements and selective chemical extractions. Based on oxalate extraction, As is mainly associated with amorphous Fe oxides through the soil profile, except in the topsoil horizons where As is hosted by another phase. SEM-EDS and EPMA analyses led to the identification of arseniosiderite (Ca 2Fe 3+ 3(As VO 4) 3O 2·3H 2O), a secondary mineral that forms upon oxidation of primary As-bearing minerals like arsenopyrite, in these topsoil horizons. These mineralogical and chemical results were confirmed by synchrotron-based X-ray absorption spectroscopy. XANES spectra of soil samples indicate that As occurs exclusively as As(V), and EXAFS results yield direct evidence of changes in As speciation with depth. Linear combination fits of EXAFS spectra of soil samples with those of various model compounds indicate that As occurs mainly As-bearing Fe(III)-(hydr)oxides (65%) and arseniosiderite (35%) in the topsoil horizon (0–5 cm depth). Similar analyses also revealed that there is very little arseniosiderite below 15 cm depth and that As(V) is associated primarily with amorphous Fe oxides below this depth. This vertical change of As speciation likely reflects a series of chemical reactions downward in the soil profile. Arseniosiderite, formed most likely by oxidation of arsenopyrite, is progressively dissolved and replaced by less soluble As-bearing poorly ordered Fe oxides, which are the main hosts for As in well aerated soils.

Depleted uranium mobility and fractionation in contaminated soil (Southern Serbia).

During the Balkan conflict in 1999, soil in contaminated areas was enriched in depleted uranium (DU) isotopic signature, relative to the in-situ natural uranium present. After the military activities, most of kinetic DU penetrators or their fragments remained buried in the ground in certain geomorphological and geochemical environments exposed to local weathering conditions. The contamination distribution, mobility and/or fixation of DU in the contaminated soil profile at one hot spot were the subject of our study. The results should disclose what happened with released DU corrosion products in three years elapsed, given the scope of their geochemical fractionation, and mark out the most probable host substrates in investigated soil type. Gamma-spectrometric analysis of soil samples taken in the DU penetrator impact-zone was done to obtain present contamination levels. Set of samples is subjected to five-step and three-step sequential extraction procedures, specifically selective to different physical/chemical associations in soil. The stable elements are determined in extracts by the atomic absorption spectroscopy. After the ion-exchange based uranium separation procedure, alpha-spectrometric analysis of obtained fractions was done and DU distribution in five extraction phases found from 235U/238U and 234U/238U isotopic ratios. Depleted uranium concentration falls down to the 1% of the initial value, at approximately 150 mm distance to the source. Carbonates and iron/manganese hydrous oxides are indicated as the most probable substrates for depleted uranium in the characterized soil type. Therefore, in the highly contaminated soil samples, depleted uranium is still weakly bonded and easy exchangeable. The significant levels of organic-bonded depleted uranium are found in surface soil only. Dependence of the fractionation on the contamination levels is evident. Samples with higher DU contents have shown a longer maintenance in the exchangeable phases, probably because adsorption/desorption mass transfer through the medium was not very fast. Organic-bonded, depleted uranium is present in surface soil samples due to its higher humus content. Considering geochemical composition of investigated soil, the indicating chemical associations as substrates are in agreement with some considerations based on the results for low-level waste unsaturated zones. The soil contamination with depleted uranium in investigated area is still 'spot' type and not widespread. Dependence of the fractionation on the contamination levels and presence of weakly bonded, depleted uranium in the hot spots areas is evident. A detailed study may be undertaken with suitable extractive reagents to define a bio-available fraction of depleted uranium in soil. The comparison of results for different soil types investigated by the same methodology may be useful. An applied combination of physical/chemical procedures and analysis may help in the decision making on the remediation strategy for sites contaminated with depleted uranium used in military operations.

Leaching potential and changes in components of metals in two acidic ferrisols

Two acidic ferrisols, i.e., red soil (RS) and yellow red soil (YRS), from the vicinity regions of non-ferrous ores in Hunan province of China, were leached with simulated acid rain through artificial column experiments. The results show that the total leaching mass of metals are m(Zn)>m(Cu) >m(Cd) from the original soils and m(Cd)>m(Zn) >>m(Cu) from the contaminated soils with external metals after leaching for 60 d continuously, leaching quantities of Cd and Zn from the contaminated red soil (CRS) are more than that from the contaminated yellow red soil (CYRS), but for Cu, i is almost the same. The preferential fractions for leaching are mainly in exchangeable forms, and content of exchangeable forms decreases significantly in the contaminated soil profiles. The unstable fractions of Cd, Cu and Zn in the RS and YRS increase significantly with the decrease of pH value of simulated acid rain. Changes of fractions of external Cd, Cu, and Zn in the residual CRS and CYRS profiles are significantly affected by the acidity of acid rain, too. After leaching for 60 d continuously, Cd exists mostly in exchangeable form, Cu exists mainly in exchangeable, manganese oxide-occluded and organically bounding forms, and Zn exists in residual in CRS and CYRS profiles. Most of exchangeable Cd and Zn exist only small in surface layer (0–20 cm) and are transferred to the sub-layers, contrarily, Cu accumulates mostly in the topsoil (0–20 cm) with low translocation.

Mobility and distribution of cadmium, nickel and zinc in contaminated soil profiles from Bangladesh

We investigated the mobility and distribution of cadmium (Cd), nickel (Ni) and zinc (Zn) in four contaminated soil profiles from Bangladesh. The sources of contamination of these profiles were tannery wastes, city sewage and the wastes of pharmaceutical and paper mill factories at different locations in Bangladesh. The samples were collected from the A-, B- and C-horizons of each profile: two sub-samples from the A-horizon at depths of 0–5 cm (A1) and >5 cm (A2), and one sample each from the B- and C-horizons. Soil samples were analysed for total metal content by dissolution in aqua regia followed by sequential extraction of the fractions based on their varying solubility. There were six operationally defined groups of extraction sequences: water soluble (F1), exchangeable (F2), carbonate (F3), oxide (F4), organic (F5) and residual (F6). The total concentration of Cd, Ni and Zn in the A-horizon (0–5 cm) ranged from 0.10 to 0.62, from 31 to 54 and from 85 to 838 mg kg−1, respectively. In the B- and C-horizons, the concentrations of these metals decreased many fold, particularly in the city sewage profile where the decrease for Cd and Zn was approximately fourfold. The distribution of metals among the chemical fractions depended on their total concentrations. In the A1-horizon, Cd had the highest mobility factor [MF = (F1+F2+F3)/(F1+F2+F3+F4+F5+F6) × 100] at 41–43% and Ni had the lowest at 3–13%, while Zn, showed intermediate values at 8–25%. The MF decreased with depth in all soil profiles. Among the fractions, the residual fraction contained the lowest levels of Cd but the highest levels of Ni and Zn. This state affected their relative mobility and distribution in soil profiles. Of the soil profiles, the mobility of all metals was higher in the city sewage soil than in any of the other three soils investigated, suggesting that the former may create a health risk by contaminating agricultural products and ground water as it also contained higher amounts of Cd and Zn.

The use of vetiver grass ( Vetiveria zizanioides) in the phytoremediation of soils contaminated with heavy metals

Recent research has shown that phytoextraction approaches often require soil amendments, such as the application of EDTA, to increase the bioavailability of heavy metals in soils. However, EDTA and EDTA–heavy metal complexes can be toxic to plants and soil microorganisms and may leach into groundwater, causing further environmental pollution. In the present study, vetiver grass ( Vetiveria zizanioides) was studied for its potential use in the phytoremediation of soils contaminated with heavy metals. In the pot experiment, the uptake and transport of Pb by vetiver from Pb-contaminated soils under EDTA application was investigated. The results showed that vetiver had the capacity to tolerate high Pb concentrations in soils. With the application of EDTA, the translocation ratio of Pb from vetiver roots to shoots was significantly increased. On the 14th day after 5.0 mmol EDTA kg −1 of soil application, the shoot Pb concentration reached 42, 160, 243 mg kg −1 DW and the root Pb concentrations were 266, 951, and 2280 mg kg −1 DW in the 500, 2500 and 5000 mg Pb kg −1 soils, respectively. In the short soil leaching column (9.0-cm diameter, 20-cm height) experiment, about 3.7%, 15.6%, 14.3% and 22.2% of the soil Pb, Cu, Zn and Cd were leached from the artificially contaminated soil profile after 5.0 mmol EDTA kg −1 of soil application and nearly 126 mm of rainfall irrigation. In the long soil leaching experiment, soil columns (9.0-cm diameter, 60-cm height) were packed with uncontaminated soils (mimicking the subsoil under contaminated upper layers) and planted with vetiver. Heavy metal leachate from the short column experiment was applied to the surface of the long soil column, the artificial rainwater was percolated, and the final leachate was collected at the bottom of the soil columns. The results showed that soil matrix with planted vetiver, could re-adsorb 98%, 54%, 41%, and 88% of the initially applied Pb, Cu, Zn, and Cd, respectively, which may reduce the risk of heavy metals flowing downwards and entering the groundwater.

Theoretical development and analytical solutions for transport of volatile organic compounds in dual-porosity soils

Predicting the behavior of volatile organic compounds in soils or sediments is necessary for managing their use and designing appropriate remedial systems to eliminate potential threats to the environment, particularly the air and groundwater resources. In this effort, based on continuity of mass flux, we derive a mass flux boundary condition of the third type in terms of physically based mass transfer rate coefficients, describing the resistance to mass inflow of the soil–air interface, and obtain one-dimensional analytical solutions for transport and degradation of volatile organic compounds in semi-infinite structured soils under steady, unsaturated flow conditions. The advective–dispersive mass balance formulation allows for mobile–immobile liquid phase and vapor diffusive mass transfer, with linear equilibrium adsorption and liquid–vapor phase partitioning in the dynamic and stagnant soil regions. The mass transfer rate coefficients of volatile organic chemicals across the soil–air interface are expressed in terms of solute properties and hydrodynamic characteristics of resistive soil and air-boundary layers. The solutions estimate solute vapor flux from soil surface and describe mobile-phase solute concentration as a function of depth in the soil and time. In particular, solutions were derived for: (1) zero-initial concentration in the soil profile subject to a continuous and pulsed source at the soil surface; and (2) depletion from the soil following an initially contaminated soil profile. Sensitivity analysis with respect to different dimensionless parameters is conducted and the effect on solute concentration and vapor flux of such parameters as volatilization mass transfer velocity relative to infiltration, soil Peclet number, biochemical decay, and diffusive mass transfer into the immobile phase, is plotted and the results are discussed. The mass transfer rate coefficients and the analytical solutions are applied to simulate transport of an example volatile organic compound in an aggregated soil. The simulated results indicate that macropore-aggregate vapor phase diffusion may profoundly impact transport of volatile compounds in aggregated soils.

In situ biodegradation of petroleum hydrocarbons in frozen arctic soils

In this in situ study performed at a hydrocarbon contaminated site at Longyearbyen, Spitsbergen, temperatures down to 6.6 m and soil gas composition of O 2, CO 2 and VOC at depths of 0.7, 2.0 and 3.5 m at the plume site (B) and the less contaminated site (R) were followed from the beginning of October to the middle of February. Soil samples from the actual depths at B and R were characterised by soil chemical parameters, nutrients, hydrocarbon concentration and enumeration of relevant microbial populations. The objective of the study was to assess whether in situ biodegradation of hydrocarbons was taking place in the contaminated frozen soil and to follow a possible reduction in the degradation activity in the following winter months. From the results we concluded that zero degrees are not an ultimate limit for in situ biodegradation of hydrocarbons by cold-adapted microorganisms and that biodegradation may proceed with the same activity at subzero temperatures. From the comparison between calculated and measured reaeration of the hydrocarbon contaminated soil profile it appeared that biodegradation of hydrocarbons may also proceed at subzero temperatures during the winter at this arctic site. The observations in this study increase the possible scenarios concerning temperature design and effects in future in situ bioremediation strategies in arctic soil.

Determination of alpha contaminated soil profiles using Nuclear Track Detectors

Nuclear Track Detectors (NTD's) are a useful option forin situ measurements of the distribution of alpha contamination as a function of soil depth. The contamination profile of alpha emitting elements, e.g. Pu, Am and U, can be determined by detecting their alpha emission at varying depths. This paper discusses a “stake” type device, containing strips of CR-39 (allyl diglycol carbonate) that can be inserted into the soil up to ten centimeters or more, depending on the firmness of the soil. The CR-39 is exposed directly to the contaminated soil for a few hours. The “stake” is then withdrawn from the soil, the plastic detectors recovered and the alpha tracks developed by chemical etching with KOH. The distribution of tracks can be used to determine the alpha contamination depth profile as well as for detecting hot spots. It has a sensitivity of less than a pCi/g of soil.

Transport of complexed cyanide in soil

Contamination of soil with cyanide, generally in the form of iron cyanide complexes [Fe(CN) 6 3− and Fe(CN) 6 4−], is commonly found at several types of industrial sites. The risks for human health or the environment posed by such sites are largely determined by the chemical behaviour and transport of complexed cyanide in soil. In acidic soil this behaviour is probably dominated by equilibrium with Prussian blue, Fe 4(Fe(CN) 6) 3(s), which is sparingly soluble under acidic conditions and limits dissolved cyanide concentrations and mobility. However, at pH levels higher than about 7 the solubility of this precipitate is extremely high, which allows cyanide to be very mobile under such conditions. Nevertheless, according to field observations, Prussian blue appears to persist for decades in alkaline soils. In this paper multicomponent transport calculations, including equilibrium with Prussian blue, iron hydroxide and relevant redox reactions, are compared with the situation as observed in two contaminated soil profiles. In case of an acidic soil, there appears to be good agreement between the calculations and the field situation. Here the mobility of cyanide is mainly regulated by the pH and redox potential and is relatively low. In case of an alkaline soil, precipitation of Prussian blue will not take place and cyanide will be very mobile once leached from the initial waste material. In this case the dissolution rate of Prussian blue is the process which determines cyanide concentrations in the groundwater. The calculations show that this dissolution rate is determined by the acid neutralizing capacity of the solution infiltrating in the waste material. The buffer capacity depends on the soil composition and can easily be so low that complete dissolution of Prussian blue may take decades. This very likely explains the persistence of this material in alkaline soils.