Impact of pasture contamination by copper,chromium, and arsenic timber preservative on soil microbial properties and nematodes

Microbial properties and nematode abundance were measured along a gradient of increasing Cu, Cr, and As concentrations (50–1300 mg Cr kg^-1) in the top 5 cm of a pasture soil contaminated by runoff of preserving liquor from an adjacent timber-treatment plant. Microbial biomass C and N were significantly (P<0.05) lower in contaminated than uncontaminated soils. The amount of microbial biomass C as a percentage of total organic C declined significantly (r ² value with Cr 0.726^*) with increasing contamination, and the ratio of respired C to biomass C was significantly (P<0.05) higher with contamination. Substrate-induced respiration, microbial biomass P, and denitrification declined (r² value with Cr 0.601, 0.833^*, and 0.709^*, respectively) with increasing contamination. Increasing contamination had no effect on prokaryote substrate-induced respiration but eukaryote: eukaryote substrate-induced respiration declined significantly (r ² value with Cr 0.722^*). Accordingly, the ratio of prokaryote substrate-induced respiration increased significantly (r ² value with Cr 0.799^*) with contamination. There was a significant (r ² value with Cr 0.872^*) hyperbolic relationship between sulphatase activity and contamination, with activity declining by approximately 80% at >1000 mg Cr kg^-1. Increasing contamination had no effect on basal respiration, dimethyl sulphoxide reduction, and phosphatase, urease, and invertase activities. Numbers of plant-associated nematodes declined significantly (r ² value with Cr 0.780^*) with contamination. On a percentage basis, plant-feeding nematodes predominated in less contaminated soils, whereas bacterial-feeding and predatory nematodes predominated in heavily contaminated soils. The use of the fumigation—incubation procedure for measurement of microbial biomass C in heavy-metal contaminated soils is discussed.     

Chromium-resistant microorganisms isolated from evaporation ponds of a metal processing plant

Chromium occurs naturally at trace levels in most soils and water, but disposal of industrial waste and sewage sludge containing chromium compounds has created a number of contaminated sites, which could pose a major environmental threat. This study was conducted to enumerate and isolate chromium-resistant microorganisms from sediments of evaporation ponds of a metal processing plant and determine their tolerance to other metals, metalloids and antibiotics. Enumeration of the microbiota of Cr-contaminated sediments and a clean background sample was conducted by means of the dilution-plate count method using media spiked with Cr(VI) at concentrations ranging from 10 to 1000 mg L^?1. Twenty Cr(VI) tolerant bacterial isolates were selected and their resistance to other metals and metalloids, and to antibiotics was assessed using a plate diffusion technique. The number of colony-forming units (cfu) of the contaminated sediments declined with increasing concentrations from 10 to 100 mg L^?1 Cr(VI), and more severely from 100 to 1000 mg L^?1 Cr(VI). The background sample behaved similarly to 100 mg L^?1 Cr(VI), but the cfu declined more rapidly thereafter, and no cfu were observed at 1000 mg L^?1 Cr(VI). Metals and metalloids that inhibited growth (from the most to least inhibitory) were: Hg > Cd > Ag > Mo = As(III) at 50 μg mL^?1. All 20 isolates were resistant to Co, Cu, Fe, Ni, Se(IV), Se(VI), Zn, Sn, As(V), Te and Sb at 50 μg mL^?1 and Pb at 100 μg mL^?1. Eighty-five percent of the isolates had multiple antibiotic resistance. In general, the more metal-tolerant bacteria were among the more resistant to antibiotics. It appears that the Cr-contaminated sediments may have enriched for bacterial strains with increased Cr(VI) tolerance.     

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.     

Chemical and microbial properties in contaminated soils around a magnesite mine in northeast China

We measured soil chemical and microbial properties at a depth of 0–20 cm among mine tailings, abandoned mined land, contaminated cropland, and uncontaminated cropland around a magnesite mine near Haicheng City, Liaoning Province, China. The objective was to clarify the impact of Mg on the soils. We found that soluble Mg²⁺ concentration and pH were significantly higher in contaminated soils (266–345 mg kg⁻¹ and 9·9–10·3, respectively) than in uncontaminated soils (140 mg kg⁻¹ and 7·1, respectively). Soil nutrients (total N, total P, mineral N, available P and soluble Ca) and microbial biomass C and N decreased as pH and soluble Mg²⁺ concentration increased. In addition, an increase of microbial metabolic quotient and a decrease of N mineralization rate were found in contaminated soils. Soluble Mg²⁺/Ca²⁺ ratios in contaminated soils were 3·5–8·9‐times higher than in uncontaminated soils. Our results indicate that soil contamination in such magnesite mine regions is characterized by high pH, Mg²⁺ concentration and soluble Mg²⁺/Ca²⁺ ratio, and low microbial activity and N and P availability. Future soil amelioration in the magnesite regions should consider applying acid ameliorants to neutralize high pH and applying calcareous ameliorants to increase Ca²⁺ concentration. Copyright © 2011 John Wiley & Sons, Ltd.     

Treatment of Cr(VI)-spiked soils using sulfur-based amendments

The objective of this research was to assess the hexavalent chromium (Cr(VI)) reducing efficiency of sulfur-based inorganic agents including calcium polysulfide (CPS), iron sulfide (FeS), pyrite (FeS₂) and sodium sulfide (Na₂S) in three soils. An alkaline soil (soil 1), a neutral soil (soil 2) and a slightly acid soil (soil 3) constituted the investigated soils. The soils were spiked with two levels of Cr(VI) (100 and 500 mg Cr(VI) kg^?1 soil) and incubated at field capacity (FC) for one month. Then, CPS, FeS, FeS₂ and Na₂S were added at 0, 5 and 10 g kg^?1 and the concentrations of exchangeable Cr(VI) were measured after 0.5, 4, 48 and 168 h in a batch experiment. The pH and organic carbon content of the soils played predominant role in Cr(VI) self-reduction by the soil itself. Complete self-reduction of Cr(VI) from soils 1, 2 and 3 was achieved at maximum Cr(VI) levels of 1, 50 and 500 mg kg^?1, respectively. Therefore, the concentration of Cr(VI) should not exceed the given levels in order to ensure that Cr(VI) is not released into the environment from contaminated sites. Moreover, decreasing pH in the alkaline soil caused significant increase of Cr(VI) reducing efficiency. Na₂S, CPS and FeS, in contrast to FeS₂, were efficient Cr(VI) reducing agents in all three soils. For all added amendments the following order of Cr(VI) reducing capacity was observed: Na₂S > CPS > FeS > FeS₂ in soil 1, Na₂S ? CPS ~ FeS > FeS₂ in soil 2 and Na₂S ? FeS > CPS ~ FeS₂ in soil 3.     

Resistance of microbial populations in DDT-contaminated and uncontaminated soils

One DDT-contaminated soil and two uncontaminated soils were used to enumerate DDT-resistant microbes (bacteria, actinomycetes and fungi) by using soil dilution agar plates in media either with 150 μg DDT ml⁻¹ or without DDT at different temperatures (25, 37 and 55°C). Microbial populations in this study were significantly (p<0.001) affected by DDT in the growth medium. However, the numbers of microbes in long-term contaminated and uncontaminated soils were similar, presumably indicating that DDT-resistant microbes had developed over a long time exposure. The tolerance of isolated soil microbes to DDT varied in the order fungi>actinomycetes>bacteria. Bacteria from contaminated soil were more resistant to DDT than bacteria from uncontaminated soils. Microbes isolated at different temperatures also demonstrated varying degrees of DDT resistance. For example, bacteria and actinomycetes isolated at all incubation temperatures were sensitive to DDT. Conversely fungi isolated at all temperatures were unaffected by DDT.     

Improvement of biochar capability in Cr immobilization via modification with chitosan and hematite and inoculation with Pseudomonas putida

ABSTRACT

Modification of biochar using chitosan and hematite made the biochar product more effective for hexavalent chromium (Cr (VI)) reduction in contaminated soils. Release experiment was conducted to examine Cr (VI) reduction in different treatments (control, unmodified biochar and two modified biochars with chitosan or hematite). The results indicated that the application of all treatments significantly decreased the release rate of Cr in comparison to the control treatment. Chitosan-modified biochar application increased Cr (VI) reduction from 28.53% (biochar) to 46.23%. In the case of hematite-modified biochar, it increased Cr (VI) reduction from 28.55% (biochar) to 38.95%. Two kinetic equations including pseudo-first-order and pseudo-second-order models employed to describe the time-dependent Cr release data. Between the kinetic equations estimated, the pseudo-second order best fitted to experimental data. In the presence of Pseudomonas putida, cumulative Cr release rate decreased by 2.38 mg kg^?1 (50.29%) in hematite–biochar and 1.768 mg kg^?1 (39.73%) in unmodified biochar as compared with control (4.43 mg kg^?1). According to results reported herein, modification of biochar with chitosan or hematite is promising since made biochar more effective in removing Cr from Cr-polluted calcareous soils.     

Response of microbial communities to different doses of chromate in soil microcosms

The toxic effect of chromate on soil microbial communities is not well documented, although microorganisms control biogeochemical cycling, contribute to formation of soil structure, regulate the fate of organic matter applied to soil. In this study the effects of short- and middle-term chromate on the soil microbial community were investigated. The shifts in the size and in the diversity of culturable heterotrophic bacterial community, the resistance to Cr(VI) of heterotrophic bacteria, the presence of cyanobacteria, the activity of 19 enzymes, and the ATP content were monitored over time (120 days) in soil microcosms artificially contaminated with three concentrations of chromate (50, 250 and 1000 mg kg⁻¹ soil). The chromate contamination affected the structure and the diversity of the soil bacterial community. Bacterial strains isolated from the microcosm contaminated with the highest concentration of chromate were identified by 16S rDNA gene sequencing. All isolates belonged to the genus Pseudomonas, were able to reduce Cr(VI), and showed a high resistance to chromate. To our knowledge, this is the first report that shows Pseudomonas strains having the capability to resist up to 40 mM of Cr(VI) on minimal medium. The cyanobacterial group was more sensitive to chromate contamination than culturable heterotrophic bacteria. No cyanobacterial growth was detected in enrichment cultures from the soil polluted with the highest chromate concentration. Some enzymes were inhibited by high concentrations of chromate, whereas others were stimulated. The ATP content in microcosms was strongly affected by chromate. We conclude that the soil microbial community responds to chromate pollution through changes in community structure, in metabolic activity, and in selection for Cr(VI)-resistance.     

Isolation of Cadmium-Resistant Bacteria and Their Resistance Mechanisms

In the first series of studies aimed at addressing the environmental problems of soils and drainage systems, we attempted to isolate cadmium (Cd)-resistant bacteria from soils heavily contaminated with Cd and determine their growth rate in media with cadmium. In soils contaminated with heavy metals, there was on increase in the number of Cd-resistant bacteria. Among 14 Cd-resistant bacteria isolated from soils contaminated with heavy metals, only six strains (Flavobacterium sp., Comamonas testosteronii, Methylobacterium fujisawaense, Alcaligenes piechaudii, Alcaligenes xylosoxidans) were identified as new types of Cd-resistant bacteria. All the isolated resistant bacteria grew fast, and reached the maximum growth rates within 24 to 48 h (Growth conditions were as follows. Culture medium: nutrient broth, pH: 6.0, temperature: 30°C and of concentration of added Cd: 0.1, 1.0, 10.0, and 100.0 mg kg^-1).     

Chromate Generation by Chromate Depleted Subsurface Materials

Soluble chromate concentrations as high as 200 μg Cr L^-1 have been reported in water samples from monitoringwells tapping alluvial deposits allegedly contaminated bylaboratory waste as well as control wells off site andupgradient (shallow aquifer) near Davis California, U.S.A. In this report we present evidence that these Cr(VI) levelscould have been generated by geogenic processes rather thanby anthropogenic inputs. We tested the hypothesis thatnative Cr(III) has been and can be oxidized to chromate bynative manganese oxides. Twenty-three drill core samples(all unsaturated) were retrieved from depths varying from1.5 to 22.5 m in 6 different wells. Visible nodules ofMnO₂ were dispersed throughout many of the samples andcarbonates were also present. Sample pH values averagedabout 8.0 and organic C was mostly less than 1.0 g kg^-1. Total Mn and Cr averaged 835 and 191 mg kg^-1respectively. All samples had the capability to oxidizeadded Cr(III) to Cr(VI). To determine the inherent capabilityof the samples to produce Cr(VI) from native Cr(III), subsamples were extracted with 5 mM CaSO₄ plus 5 mM MgSO₄ until Cr(VI) was no longer detected. After freeze-drying, deionized-distilled water was added to theleached samples to approximately field capacity (0.03 MPa). Freeze drying did not generate Cr(VI). These samples wereincubated in polyethylene film bags at room temperature inthe dark. After 1 week incubation, water in the samples wasextracted by centrifugation and the extracts were analyzedfor Cr(VI). All of the samples generated Cr(VI), and theconcentrations in the extracts ranged from 20 to 100 μg Cr L^-1. Total chromium, endemic chromium VI and chromium VI generated in leached samples were not statistically different between samples from onsite and control samples taken offsite and upgradient in respect to the shallowest aquifer.     

Sorption Characteristics of Chromium and Its Phytotoxic Effect with or without City Compost on Maize and Spinach in a Vertisol of Central India

Abstract

Phytotoxicity, due to chromium [Cr (VI)] additions from low to very high levels in a swell–shrink clayey soil (Haplustert), in maize and spinach was studied in a pot culture experiment. Six levels of Cr (VI) (0, 5, 10, 25, 50, and 75 mg kg^?1 soil) for maize and five levels for spinach (0, 2, 5, 10, and 25 mg kg^?1 soil) were applied singly and in combination with two doses (0 and 20 t ha^?1) of city compost. At levels of more than 75 mg Cr (VI) kg^?1 soil for maize there was virtually no growth after germination, whereas 25 mg Cr (VI) kg^?1 soil hindered the germination of spinach crop. Initial symptoms of Cr (VI) toxicity appeared as severe wilting of the tops of treated plants. Maize plants suffering from severe Cr (VI) toxicity had smaller roots and narrow brownish red leaves covered with small necrotic spots. In spinach, severe chlorosis was observed in leaves. Higher levels of Cr (VI) inhibited the growth and dry‐matter yield of the crops. However, application of city compost alleviated the toxic effect of Cr (VI). The concentration of Cr (VI) in plant parts increased when Cr (VI) was applied singly but decreased considerably when used in combination with city compost. There was evidence of an antagonistic effect of Cr (VI) on other heavy‐metal (Mn, Cu, Zn, and Fe) concentrations in plant tops. Thus, when Cr (VI) concentration increases, the concentration of other beneficial metals decreases. Chromium (VI) concentration in maize roots ranged from traces (control) to 30 mg kg^?1and were directly related to soil Cr (VI) concentration. At 25 mg Cr (VI) kg^?1 soil, yield of maize was reduced to 41% of control plants, whereas in spinach, 10 mg Cr (VI) kg^?1 soil caused a 33% yield reduction. Experimental results revealed that the maize top (cereal) is less effective in accumulating Cr (VI) than spinach (leafy vegetables). Laboratory studies were also conducted to know Cr (VI) sorption capacity of a swell–shrink clayey soil with and without city compost, and it was found that Cr (VI) sorption reaction was endothermic and spontaneous in nature.     

Copper Accumulations in Soils,Coffee, Banana,and Bean Plants Following Copper-Based Fungicides in Coffee Farms in Arusha and Kilimanjaro Regions,Tanzania

This study was carried out to investigate the levels of copper (Cu) contamination in coffee fields in Kilimanjaro and Arusha regions, Tanzania, to increase the database on the contamination of soils by Cu-based fungicides in coffee fields. Surface (0–20 cm deep) soil samples were collected from different farms in Kilimanjaro and Arusha regions. Coffee, banana, and bean plant samples were collected from the locations of soil sampling. Soil and plant samples were analyzed at the Department of Soil Science, Sokoine University of Agriculture, Morogoro, Tanzania. It was found that the calcium chloride (CaCl₂)–extractable Cu was less than the detection limit of flame atomic absorption spectrometry. Diethylenetriaminepentaacetic acid (DTPA)–extractable (24 to 366 mg Cu kg^?1 soil) and aqua regia–extractable (80 to 806 mg Cu kg^?1 soil) Cu levels were high enough to raise environmental alarm (based on European Union guidelines) in the Cu fungicide–treated soils as compared with natural Cu levels in untreated soils (1 to 12 mg Cu kg^?1 soil for DTPA and 22 to 32 mg Cu kg^?1 soil for aqua regia–extractable Cu). Coffee, banana, and bean plants grown on soils contaminated by Cu fungicides had varied concentrations of Cu that were greater than the concentrations of Cu in the plants collected from the uncontaminated soils. Stepwise regression analysis carried out to investigate the relationships between the soil properties and the concentrations of Cu in plants revealed a significant (P = 0.01) positive relationship (R² = 0.4) between organic carbon and the concentration of Cu in banana leaves. Aqua regia–extractable Cu was positively correlated (P = 0.03, R² = 0.4) with the concentrations of Cu in banana leaves. For bean leaves, electrical conductivity (EC) had a positive significant (P = 0.01) relationship (R² = 0.56) with the concentrations of Cu in the plants. It is recommended that further research be carried out to investigate the dynamics and bioavailability of Cu for the different crops interplanted in the coffee fields.     

Hexavalent Chromium Dynamics and Uptake in Manure-Added Soil

The soil dynamics of hexavalent Cr, a particularly mobile and toxic metal, is of a great environmental concern, and its availability to plants depends on various soil properties including soil organic matter. Thus, in a pot experiment, we added 50?mg Cr(VI) kg^?1 soil and studied Cr(VI) soil extractability and availability to spinach, where we applied both natural (zeolite), synthetic adsorptive materials (goethite and zeolite/goethite) and organic matter with farmyard manure. We found that, compared to the unamended control plants, dry matter weight in the Cr(VI)-added soil was greatly decreased to 17?% of the control, and height was decreased to 34?% of the control, an indication of Cr toxicity. Also, exchangeable Cr(VI) levels in soil decreased back to the unamended control even in the first soil sampling time. This was much faster than the exchangeable Cr(VI) levels in the mineral-added soil, where Cr(VI) levels were decreased to the levels of the unamended control in the third sampling time. The positive effect of organic matter was also indicated in the Cr quantity soil-to-plant transfer coefficient (in grams of Cr in plant per kilogram of Cr added in soil), a phyto-extraction index, which was significantly higher in the manure-amended (1.111?g?kg^?1) than in the mineral-added treatments (0.568?g?kg^?1). Our findings show that organic matter eliminates the toxicity of added Cr(VI) faster than the mineral phases do and enhances the ability of spinach to extract from soil greater quantities of Cr(VI) compared to mineral-added soils.     

Critical Toxic Ranges of Chromium in Spinach Plants and in Soil

ABSTRACT

Long-term irrigation with untreated industrial sewage effluents causes accumulation of high concentrations of chromium (Cr) and other heavy metals in soil and subsequently in crop plants (especially leafy vegetables), which can be phytotoxic to plants and/or a health hazard to animals and humans. Greenhouse experiments were conducted to determine the effects of Cr application on the growth of spinach (Spinacia oleracia L.) and to develop critical toxic ranges of Cr in plants and in soil. The study involved growing of spinach variety ‘Punjab Green’ in a greenhouse on silty clay loam and sandy soils equilibrated with different levels of applied Cr (0, 1.25, 2.5, 5, 10, 20, 40, 80, 160, and 320 mg Cr kg^{? 1} soil). Plants were harvested at: three growth stages 45, 60, and 90 days after sowing (DAS). Critical toxic ranges were estimated by regressing and plotting data on ammoniumbicarbonate-diethylenetriaminepenta-acetic acid (AB-DTPA) extractable Cr in soil or Cr concentration in plants versus dry-matter yield (DMY) of spinach at the three growth stages. Toxic ranges, i.e., slightly toxic (80%–90%), moderately toxic (70%–80%), and extremely toxic (< 70%) in terms of DMY relative to the attainable maximum DMY, were established for both soils and for plants at all three growth stages. There was no germination of spinach with applied Cr at 320 mg Cr kg^{? 1} rate in silty clay loam soil and at 40 mg Cr kg^{? 1} rate in sandy soil due to Cr toxicity. Roots accumulated more Cr in comparison with shoots. Chromium concentrations of 0.47–1.93 mg Cr kg^{? 1} soil in silty clay loam soil, 0.13–0.94 mg Cr kg^{? 1} soil in sandy soil, 1.08–5.40 mg Cr kg^{? 1} plant DM in silty clay loam soil and 0.54–11.7 mg Cr kg^{? 1} plant DM in sandy soil were found to be toxic. The critical toxicity ranges of Cr thus established in this study could help in demarcating Cr toxicity in soils and in plants such as spinach and other leafy vegetables due to irrigation of soils with untreated sewage water contaminated with chromium.     

Arsenic resistant microorganisms isolated from agricultural drainage water and evaporation pond sediments

Elevated levels of As in contaminated water and soil could pose a major threat to the environment. Relatively high levels of As have been reported in agricultural drainage water and in evaporation pond sediments in Kern County, California. The objective of this study was to enumerate and isolate As-resistant microorganisms from agricultural drainage water and evaporation pond sediments and to assess their tolerance to metals, metalloids and antibiotics. The culture medium was amended with arsenite (III), arsenate (V), methylarsonic acid (MAA), and dimethylarsinic acid (DMA). Among the water samples, As(V), MAA, and DMA added to the medium at concentrations from 0.1 to 1000 mg L^?1 showed no effect on the colony forming units (CFUs) compared with no As supplementation, while arsenite (III) (> 1.0 mg L^?1) inhibited the population. The sediments showed three trends: (i) no effect on CFUs in the presence of As(V) up to 1000 mg kg^?1, (ii) a decline in CFUs in the presence of > 100 mg kg^?1, As(III), and (iii) an increase in CFUs upon the addition of MAA or DMA at > 25 mg kg^?1, Arsenite (III) was much more toxic to the indigenous microflora than any other As species. Arsenite (III) inactivates many enzymes by having a high affinity for thiol groups of proteins. A plate diffusion method was used to assess the tolerance of the As-resistant bacteria to heavy metals, metalloids and antibiotics. Of 14 isolates tested, all were resistant to Co, Cu, Pb, Ni, Mo, Cr, Se(IV), Se(VI), As(III), As(V), Sb, Sn, and Ag (50 µg mL^?1). The most toxic trace elements were Cd followed by Hg>Te>Zn. Multiple antibiotic tolerance (resistance to 2 or more antibiotics) was found among 43% of the isolates. The As-resistant bacteria showed a high tolerance to metals and antibiotics.     

Use of the BCR three-step sequential extraction procedure for the study of the partitioning of Cd, Pb and Zn in various soil samples

A slightly modified three-step sequential extraction procedure proposed by the Community Bureau of Reference (BCR) for analysis of sediments was successfully applied to soil samples. Contaminated soil samples from the lead and zinc mining area in the Mezica valley (Slovenia) and natural soils from a non-industrial area were analysed. The total concentrations of Cd, Pb and Zn and their concentrations in fractions after extraction were determined by flame or electrothermal atomic absorption spectrometry (FAAS, ETAAS). Total metal concentrations in natural soils ranged from 0.3 to 2.6 mg kg^-1 for Cd, from 20 to 45 mg kg^-1 for Pb and from 70 to 140 mg kg^-1 for Zn, while these concentrations ranged from 0.5 to 35 mg kg^-1 for Cd, from 200 to 10000 mg kg^-1 for Pb and from 140 to 1500 mg kg^-1 for Zn in soils from contaminated areas. The results of the partitioning study applying the slightly modified BCR three-step extraction procedure indicate that Cd, Pb and Zn in natural soils prevails mostly in sparingly soluble fractions. Cd in natural soils is bound mainly to Fe and Mn oxides and hydroxides, Pb to organic matter, sulphides and silicates, while Zn is predominantly bound to silicates. In contaminated soils, Cd, Pb and Zn are distributed between the easily and sparingly soluble fractions. Due to the high total Cd, Pb and Zn concentrations in contaminated soil close to the smelter, ! and their high proportions in the easily soluble fraction (80% of Cd, 50% of Pb and 70% of Zn), the soil around smelters represents an environmental hazard.     

Stabilization of chromium(VI) by hydroxysulfate green rust in chromium(VI)-contaminated soils

Chromium (Cr)-contaminated soils pose a great environmental risk, with high solubility and persistent leaching of Cr(VI). In this study, hydroxysulfate green rust (GR_SO4), with the general formula Fe(II)₄Fe(III)₂(OH)₁₂SO₄·8H₂O, was evaluated for its efficiency in Cr(VI) stabilization via Cr(VI) reduction to Cr(III) in four representative Cr(VI)-spiked soils. The initial concentrations of phosphate buffer-extractable Cr(VI) (Cr(VI)_b) in soils 1, 2, 3, and 4 were 382.4, 575.9, 551.3, and 483.7 mg kg^-1, respectively. Reduction of Cr(VI) to Cr(III) by structural Fe(II) (Fe(II)_s) in GR_SO4 in all studied soils was fast, wherein the application of GR_SO4 markedly decreased the amount of Cr(VI)_b at the Cr(VI)_b/Fe(II)_s stoichiometric mole ratio of 0.33. The kinetics of Cr(VI) reduction by GR_SO4 could not be determined as this reaction coincided with the release of Cr(VI) from soil during the experiment. The concentration of Cr(VI)_b decreased, as the Cr(VI)_b/Fe(II)_s ratio decreased from 0.46 to 0.20, generally to below 10 mg kg^-1. Back-transformation of the generated Cr(III) was examined in the presence of manganese oxide birnessite at the birnessite/initial Cr(III) mole ratio of 4.5. The results of batch tests showed that only 5.2% of the initial Cr(III) was converted to Cr(VI) after two months, while under field capacity moisture conditions, less than 0.05% of the initial Cr(III) was oxidized to Cr(VI) after six months. The results illustrated that remediation of Cr(VI)-contaminated soils would be fast, successful, and irreversible with an appropriate quantity of fresh GR_SO4.     

Impact of pasture contamination by copper,chromium, arsenic timber preservative on soil biological activity

Contamination of grazed pasture gave 0–5 cm soil contents of 19–835 mg kg^-1 Cu, 47–739 mg kg^-1 Cr, and 12–790 mg kg^-1 As. Soil Cu, Cr, As contents were correlated and declined with depth to 30 cm. In plots with medium and high contamination buried cotton strips retained most of their original tensile strength, indicating repression of decomposition processes.Lumbricus rubellus andAporrectodea rosea were absent in plots with medium and high contamination; there was no evidence of heavy metal accumulation in earthworm tissue; soil bulk density was greater in the absence of lumbricids. Enchytraeids and nematodes were most abundant with low contamination. Nematode diversity was greater with low (0–5 cm) or medium (5–10 cm) contamination than in control plots or those with high contamination; the proportion of predators increased with contamination. Basal soil respiration was less sensitive than substrate-induced respiration to contamination. Although contamination reduced the nitrification rate, all mineral N was found as NO _inf3 ^sup- after 14 days. Sulphatase was the enzyme activity most sensitive to high contamination. Whereas contamination by 100 mg kg^-1 of Cu, Cr, and As caused little depression of soil biological activity, there was some supperssion at 400 mg kg^-1 and at 800 mg kg^-1 normal processes were inhibited and herbage production was negligible. No single measurement adequately indicated the need for site remediation.     

Characterization of chromium-containing wastes and soils affected by the production of chromium tanning agents

Purpose

Wastes of unknown composition derived from the production of trivalent chromium (Cr(III)) salts used as tanning agents are deposited in the area of Kanpur, India. The questions of whether these samples are chromite ore processing residue (COPR) and whether Cr occurs in its toxic hexavalent form (Cr(VI)) arise.

Materials and methods

Twenty-one samples from two disposal sites and surrounding soils were analyzed, specifically examining their elemental and mineralogical composition. Additionally, aqueous eluates with different liquid-to-solid ratios were performed and analyzed for Cr(VI).

Results and discussion

The samples were classified in accordance to the sum of silicon and aluminum and the sum of calcium and Cr contents: uncontaminated, moderately contaminated, and highly contaminated material. Highly contaminated material exhibited extremely alkaline pH values up to 12.5 and total Cr contents ranging from 65.7 to 110 g/kg, whereas uncontaminated material had comparatively moderate pH values and Cr contents <1 g/kg. In total, seven crystalline phases commonly found in COPR were identified in the contaminated samples, of which five phases (brownmillerite, hydrocalumite, hydrogarnet, magnesiochromite, and periclase) are known to be able to accommodate Cr whereas hydrogarnet and hydrocalumite are the main host phases for Cr(VI). Batch tests showed that dissolution controlled the Cr(VI) concentrations in the eluates.

Conclusions

Six samples were clearly identified as highly Cr-contaminated COPR. Leaching of Cr(VI) and resulting contamination of soils and water bodies is a key environmental risk arising from these COPR sites especially during the monsoon season. This situation is of particular concern as the local population use the highly Cr(VI)-contaminated water not only for the needs of livestock and irrigation but also as drinking water due to the absence of alternative water resources.     

不同类型表面活性剂增效去除焦化厂污染土壤中多环芳烃的研究

Surfactant enhanced remediation is thought to be an effective method for the remediation of soils polluted with hydrophoblc organic compounds. Desorption of polycyclic aromatic hydrocarbons （PAHs） from an abandoned manufactured gas plant （MGP） soil was evaluated using four eluting agents including Triton X-100 （TX100）, sodium dodecylbenzene sulfonate （SDBS）, rhamnolipid water solution （RWS） and rhamnolipid fermentation broth （RFB）. The weight solubilization ratios for acenaphthene and fluorene were in the order of TX100 〉 SDBS 〉 RWS 〉 RFB. The Sm value, which indicates the maximum amounts of surfactants adsorbed in the soil, was in the order of RWS 〉 RFB 〉 SDBS 〉 TX100. By using 8 g L-1 of TX100, SDBS and RWS and 100% of RFB, the T-PAHs removal for the MGP soil contaminated with 207.86 mg T-PAHs kg-1 dry soil was 48.0%, 45.7%, 1.9%, and 8.6%, respectively, while that decreased to 41.6%, 37%, 0.38%, and 1.3% for the soil contaminated with 3494.78 mg T-PAHs kg-1 dry soil. Only 8 g L-1 TX100 could remove all types of the 16 PAHs partly in the MGP soil, and the removal efficiencies of different PAHs ranged from 13% to 77.8%. The results of this study herein provide valuable information for the selection of TX100 surfactant for remediating PAH-contaminated soils in MGP.