Impact of shallowly deposited ore-bearing dolomites on local soil pollution aureoles of As, Cd, Pb, and Zn in an old mining area

Purpose

The study area, located in Upper Silesian Industrial Region, was rich in significant amounts of ores that were classified of Mississippi Valley type. Being these ores especially rich in Pb and Zn, an intense development of mining and ore extraction industry was verified in this area. The goal of this study was to investigate how local pollution aureoles of As, Cd, Pb, and Zn were influenced by the presence of shallowly deposited ore-bearing dolomites.

Materials and methods

Very extensive sampling campaign was carried out, and over 1,000 samples were collected in the area of about 150?km². Local aureoles of investigated metals were calculated for two soil layers. The first one covered the part of soil core from the soil surface to the depth of 20?cm and the second one from the depth of 40?cm to the depth of 60?cm. All spatial distributions of particular metals in soil were calculated by means of ordinary kriging using free softwares QGIS and SAGA.

Results and discussion

Maximum concentrations of Pb and Zn in soil in study area were very high, reaching over 24,000 and 77,000?mg/kg, respectively. Maximum concentrations of As and Cd were also very high, reaching about 1,000?mg/kg. Those maximum values were observed in the direct vicinity of the Boles?aw mine and its mine dumps. Almost all local aureoles were located within the range of ore-bearing dolomites. It was especially visible for Pb and Zn, minerals very common in ore deposits. Otherwise, local aureoles of As and Cd were more related with the vicinity of mines and other pollution sources, being more associated to the anthropogenic pollution than to the presence of ore-bearing dolomites.

Conclusions

The aureoles of Pb and Zn, and in moderate degree of As, were associated with a mineral composition of ores. Differently, the location, the shape, and spatial pattern of Cd aureoles suggest that they were mostly influenced by anthropogenic pollution. Anthropogenic factors were dominating over the lithogenic ones and masking the influence of the shallowly deposited ores.     

Identification of the sources of metals and arsenic in river sediments by multivariate analysis and geochemical approaches

Purpose

Frequent mining activities and higher background values in soil have led to the contamination of the sediments of some rivers in southwest China by several metals and arsenic (As). This study combined multivariate analysis with geochemical approaches to differentiate mining activity from other sources, which may aid to evaluate the effectiveness of reducing mining release.

Materials and methods

Sixteen sediment samples were collected along the Yuan River, China. The total concentrations of lead (Pb), zinc (Zn), copper (Cu), cadmium (Cd), chromium (Cr), mercury (Hg), and As were measured by inductively coupled plasma-atomic emission spectrometer (ICP-AES). The Pb isotopic composition was measured using a thermal ionization mass spectrometer (TIMES). Both geochemical approaches and multivariate statistical analysis were used to identify the sources of these metals. The fractionation of Pb was determined through a Community Bureau of Reference (BCR) sequential extraction procedure to aid the identification of the sources.

Results and discussion

The concentrations and enrichment factors (EFs) of Pb, Zn, Cu, Cd, and As in the middle reach of the river were higher than those at the other sites, indicating anthropogenic sources. The factor analysis (FA) extracted “mining and smelting,” “mixture of anthropogenic and natural,” and “natural” factors. The Pb isotope composition of metal ores was similar (²⁰⁶Pb/²⁰⁷Pb?<?1.190 and ²⁰⁸Pb/²⁰⁶Pb?>?2.023) to that found in the sediments in the middle reach, indicating anthropogenic sources of mining activities. Compared with the narrow ranges of the δ³⁴S ratios in the bedrock (+8.5 to +9.3?‰) and the metal ores (?1.4 to +1.9?‰), the sediment samples presented a relatively wide range of δ³⁴S ratios from ?2.6 to +9.2?‰ with a mean of +2.6?‰, which suggests a mixed composition. The BCR sequential extraction procedure revealed that the proportion of the extractable fraction in the sediments in the middle reach was higher than that in other sites, suggesting anthropogenic sources as the cause of contamination in the study area.

Conclusions

Lead, Zn, Cu, Cd, Cr, Hg, and As are mainly derived from natural materials in the upstream region. In the middle reach, these elements are the result of anthropogenic activities, particularly activities associated with the mining industry. In the downstream region, the origin of these elements is considered to be a mixture of anthropogenic and natural sources. In addition to geochemical approaches and multivariate statistical analysis, the BCR sequential extraction method is an effective procedure for the identification of the anthropogenic sources of sediment-associated metals.     

Study of the antimony species distribution in industrially contaminated soils

Purpose

The purpose of the present study was to investigate the distribution of antimony (Sb) and its species in soil fractions in order to understand better the real risk associated with Sb in the environment.

Materials and methods

Nine surface soil samples contaminated from lead/zinc and iron smelting operations and coal fired power plants were examined using: (1) four-step sequential extraction procedure (BCR); (2) two-step sequential extraction including ethylenediaminetetraacetic acid (EDTA), sodium hydroxide (NaOH) and NH₄F; and (3) single extraction with EDTA and NaOH. Liquid phase extraction was used for redox speciation of Sb. The distribution of Sb between soil fulvic and humic acids was determined after their chemical separation. The concentrations of Sb were measured by electrothermal atomic absorption spectrometry.

Results and discussion

The main part of total Sb (2.5–105 mg?kg^?1) was associated with the residual fraction in all soils. The exchangeable/carbonate-bound concentrations were 0.83–4.7 % of total Sb. Up to 6.8 % was in the reducible and up to 1.4 % was in the oxidizable fraction. EDTA removed 7.2–11.4 % of total content. Sb(V) was the predominant form in acetic acid and EDTA extracts. Single extraction with 0.1 mol?l^?1 NaOH released up to 13.7 % of soil antimony. The main part of Sb was complexed to the higher molecular weight fraction of soil-derived humic substances.

Conclusions

For highly contaminated soils, 4 % solubility in acetic acid could represent risk of contamination of ground water under specific conditions. Also, the relatively high phytoavailable Sb (7–11 %) can represent a significant proportion in highly polluted soils. Pentavalent antimony was the main antimony species extracted from soils. The main part of the organically antimony was found to be present as complexes with higher molecular weight humic acids fraction.     

Pilot-scale counter-current acid leaching process for Cu,Pb, Sb,and Zn from small-arms shooting range soil

Purpose

The main objective of this study was to evaluate the potential of a counter-current leaching process (CCLP) on 14 cycles with leachate treatment at the pilot scale for Pb, Cu, Sb, and Zn removal from the soil of a Canadian small-arms shooting range.

Materials and methods

The metal concentrations in the contaminated soil were 904?±?112 mg Cu kg^–1, 8,550?±?940 mg Pb kg^–1, 370?±?26 mg Sb kg^–1, and 169?±?14 mg Zn kg^–1. The CCLP includes three acid leaching steps (0.125 M H₂SO₄?+?4 M NaCl, pulp density (PD)?=?10 %, t?=?1 h, T?=?20 °C, total volume?=?20 L). The leachate treatment was performed using metal precipitation with a 5-M NaOH solution. The treated effluent was reused for the next metal leaching steps.

Results and discussion

The average metal removal yields were 80.9?±?2.3 % of Cu, 94.5?±?0.7 % of Pb, 51.1?±?4.8 % of Sb, and 43.9?±?3.9 % of Zn. Compared to a conventional leaching process, the CCLP allows a significant economy of water (24,500 L water per ton of soil), sulfuric acid (133 L H₂SO₄ t^–1), NaCl (6,310 kg NaCl t^–1), and NaOH (225 kg NaOH t^–1). This corresponds to 82 %, 65 %, 90 %, and 75 % of reduction, respectively. The Toxicity Characteristic Leaching Procedure test, which was applied on the remediated soil, demonstrated a large decrease of the lead availability (0.8 mg Pb L^–1) in comparison to the untreated soil (142 mg Pb L^–1). The estimated total cost of this soil remediation process is 267 US$ t^–1.

Conclusions

The CCLP process allows high removal yields for Pb and Cu and a significant reduction in water and chemical consumption. Further work should examine the extraction of Sb from small-arms shooting range.     

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.     

Multi-residue analysis of PAH, PCB, and OCP optimized for organic matter of forest soil

Purpose

Analyzing organic pollutants in forest soil is challenging because they are strongly physical and chemical bound to soil organic matter (SOM). Within the framework of a forest soil inventory, an analytical protocol for the determination of polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), and organochlorine pesticides (OCP) should be established and validated using one and the same extraction and cleanup procedure. The protocol should be applicable for reliable analysis of a high number of samples in a short timeframe.

Materials and methods

Two different soil samples representative for the humic layer from a typical mixed and coniferous forest soil had been used for the analysis. Three solvents of different polarity, namely cyclohexane (CH), ethylacetate (EA)/CH (1/1, v/v), and acetone (AC)/CH (2/1, v/v), and the six standard extraction techniques (pressurized liquid extraction (PLE), soxhlet extraction, fluidized bed extraction, sonication, shaking, and one-step extraction recommended for analyzing agricultural soil in Germany (VDLUFA 2008)) were compared concerning their extraction efficiency. For additional matrix separation, two different cleanup procedures (gel permeation chromatography (GPC) and solid-phase extraction (SPE) with different sorbents) were tested. Quantification was carried out using gas chromatography combined with mass spectrometry (GC–MS) and two different injection systems (split/splitless injection and programmable temperature vaporizer (PTV) injection). Labeled internal standards, added prior to extraction, were used for method evaluation.

Results and discussion

For the simultaneous extraction of PAH, PCB, and OCP from organic forest soil PLE with acetone/cyclohexane (2/1, v/v) provided the highest extraction efficiency. A two-step cleanup procedure consisting of GPC followed by SPE with silica gel was entirely sufficient for the separation of humic substances without discrimination of analytes. Recovery rates for the different extraction and cleanup steps ranged between 89% and 106%. For quantification, a GC–MS method was developed using two different injection systems and two capillary columns of different selectivity.

Conclusions

By comparing six standard extraction techniques for PAH, PCB, and OCP from forest soil, we obtained the highest extraction efficiency when using PLE with AC/CH (2/1). For sample injection, we achieved best results using an optimized PTV injection system as it highly reduced the breakdown of thermolabile pesticides. Using this combination of technical equipment, it is possible to determine a concentration of the analytes in the trace level range of 1–2 μg kg^?1 in humic soil.     

Numerical approach to modelling pulse-mode soil flushing on a Pb-contaminated soil

Purpose

Soil flushing can represent a suitable technology in remediation of soils, sediments and sludge contaminated by persistent species (e.g. toxic metal). This paper presents a model specifically developed to evaluate the feasibility of chelating agent-enhanced flushing. The model, here applied to the remediation of real Pb-contaminated soils, was conceived also to simulate an innovative pulse-mode soil flushing technique.

Materials and methods

The soil flushing application was firstly carried out through columns laboratory experiments. Columns were filled with a real Pb-contaminated soil (3,000 mg kg^?1 of dry soil) and flushing was operated in a pulse mode with different chelating agent dosages (3 and 4.3 mmol kg^?1soil). Experimental results were used to calibrate and validate the developed reactive transport model that accounts for transport of ethylenediamine tetraacetic acid (EDTA) and EDTA–Pb chelate complexes, Pb residual concentration on soil and the reduction in permeability by soil dissolution. Determination of hydrodynamic and hydro-dispersive parameters was carried out through a numerical approach incorporating the use of neural network as interpolating function of breakthrough data obtained by a tracer test.

Results and discussion

The EDTA dosage strongly influenced the efficiency in Pb extraction and soil permeability. Cumulative extractions of Pb were found to be 20 and 29 % for the EDTA concentrations of 3 and 4.3 mmol/kg of dry soil, respectively. The soil dissolution caused a significant flow rate decrease, as a consequence of the increase in chelating agent concentration. Therefore the recovery phase duration increased from 738 to 2,080 h. The ability of the model in simulating all the examined phenomena is confirmed by a good fit with experimental results in terms of (a) soil permeability reduction, (b) eluted Pb and (c) residual Pb in the soil.

Conclusions

Results highlighted as the model, supported by a preliminary and careful characterization of the soil, can be useful to assess the feasibility of the flushing treatment (avoiding soil clogging) and to address the choice of the operating parameters (flow rate, chelating agent dosage and application method). On the basis of the present research results, a protocol is suggested for in situ soil pulse–flushing application.     

Does the compositional change of soil organic matter in the rhizosphere and bulk soil of tea plants induced by tea polyphenols correlate with Pb bioavailability?

Purpose

Soil organic matter (SOM) plays a vital role in controlling metal bioavailability. However, the relationship between SOM and its fractions, including water-soluble substances (WSS), fulvic acid (FA), humic acid (HA), and soil microbial biomass (SMB), to metal bioavailability in plants has not been thoroughly investigated. This study examined the compositional change of SOM after tea polyphenols (TPs) were added to the soil and its correlation with Pb bioavailability.

Materials and methods

Ultisol samples were collected from Fuyang, spiked with two levels (0 and 300 mg kg^?1 DW) of Pb, and aged for 30 days. Four uniform seedlings were transplanted to each plastic pot, which were filled with 3 kg of air-dried soil. After successful transplantation, three levels (0, 300, and 600 mg kg^?1 DW) of TPs were amended as irrigation solution for the pots. The Pb concentrations in different tissues of the tea plants were determined after 6 months. SOM, WSS, FA, HA, and SMB were extracted and quantified using a Multi N/C Total Organic Carbon Analyser.

Results and discussion

Adding TPs to Pb-polluted soils alleviated Pb toxicity to microorganisms and increased SMB and the rhizosphere effect. The rhizosphere SOM was lower than bulk SOM in Pb-unspiked soils, while the opposite results were observed in Pb-spiked soils. A similar inconsistency for HA in the rhizosphere and bulk soil between Pb-unspiked and Pb-spiked soils might explain the difference in SOM. FA increased with the addition of TPs in both the rhizosphere and bulk soils, which might be the result of TP transformation. Positive correlations are present between the compositions of rhizosphere SOM and Pb in different tissues of the tea plant. SMB correlated negatively with Pb in young leaves and stems. Compared to rhizosphere soil, SOM components in bulk soil were less strongly correlated with Pb in tea plants.

Conclusions

Addition of TPs to soil changes the components of SOM and Pb bioavailability. SOM and its fractions, including WSS, FA, HA, and SMB, show a close relationship to Pb in different tissues of the tea plants.     

Evaluation and source identification of trace element contamination of soils in the Qixia lead-zinc mining area,Jiangsu, China

Purpose

The Qixia mine is one of the largest lead-zinc mines in Eastern China and has been operational for approximately 60 years. Source identification for trace element contamination of soils in the Qixia mining area has been lacking. This report details the evaluation and source identification of trace element contamination (including Cu, Zn, Pb, Cd, Hg, Cr, As, and Ni) of soils in this area.

Materials and methods

Thirty-three soil samples from roadsides and fields in the study area were collected and analyzed. The index of geo-accumulation (I _geo) was employed to evaluate contamination. Methods of multivariate statistical analysis were used to determine the probable sources of the pollutants.

Results and discussion

The analysis showed that the levels of contamination ranked in the following order: Cd > Pb/Zn> > As/Cu> > Hg > Cr/Ni. In the sampling area nearest the mine, soil samples collected from roadsides showed much higher levels of contamination than those collected from fields away from the roadways. Trace element contamination decreased as the distance from the mine increased. Contamination extended to a distance of approximately 700 m from mineral transportation routes, with the area of greatest impact at 200 m or less. Multivariate statistical analysis and ore composition data suggest that the Cu, Zn, Pb, Cd, and As found in the soil samples originate from anthropogenic sources. Ni and Cr are considered to be at natural background concentrations.

Conclusions

This study distinguished between natural and anthropogenic sources of trace element contamination in the soils of the Qixia mining area. The contamination of Cu, Zn, Pb, Cd, and As is linked to the mining activities and is likely due to the transportation of ore concentrates and tailings.     

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.     

Contamination of a boatyard for maintenance of pleasure boats

Purpose

The object of this study was to study a boat maintenance facility by investigating the degree of contamination and assessing how leachate water from soil affects organisms from three trophic levels.

Materials and methods

Surface and subsurface (20-cm depth) soil samples were collected in a typical boatyard (200 boats, 12,000 m²) at a 70- (station A), 90- (station B), 120- (station C) and 160-m (station D) distance from the shoreline. Three replicate samples, ～10 m apart, were taken at stations A, B and C, respectively, and one replicate was taken at station D (i.e. altogether 20 samples with 10 at surface and subsurface, respectively). The total copper (Cu), lead (Pb), tin (Sn) and zinc (Zn) concentrations were determined for all replicates. Pooled samples from the respective stations were used for analysis of organotin compounds, irgarol and polyaromatic hydrocarbons. Leachate waters were produced from the pooled samples and used for toxicity testing with the bacterium Vibrio fischeri, the macroalga Ceramium tenuicorne and the crustacean Nitocra spinipes.

Results and discussion

Very high concentrations of Cu, Pb, Zn were detected, with maximum values of 16,300, 6,430 and 18,600 mg/kg dw, respectively. Organic hazardous compounds were found in high concentrations with maximum values of 37, 27 and 16 mg/kg dw for tributytin (TBT), dibutyltin (DBT) and triphenyltin (TPhT), respectively. All pollutants exceeded existing guidance values for both sensitive land use and less sensitive land use by several factors, in both surface and subsurface soil. The least and worst cases of total amount of TBT (12 000 m² and 0.2 m depth) were estimated to be 10 and 122 kg of TBT. Leachates were shown to be toxic in all three test organisms.

Conclusions

Several known hazardous pollutants were found in boatyard maintenance areas and they exceeded recommended guidance values by several factors. Leachates were shown to be toxic to test organisms of several trophic orders. This underlines that boat maintenance facilities in general should be better regulated to minimize further exposure to humans and spread of contaminants in the environment. The amounts of contaminants accumulated in these areas call for investigations of how remediation should be performed.     

Fractionation of chromium in tannery sludge-amended soil and its availability to fenugreek plants

Purpose

Fenugreek (Trigonella foenum-graecum L.) is a medicinal plant with antidiabetic effects. Chromium has been related to better glucose tolerance in humans. The objective of this study was to determine whether tannery sludge could be used for Cr biofortification of fenugreek.

Materials and methods

Soil was mixed with tannery sludge containing 6.03 g Cr kg^?1. All Cr was in the form of Cr(III). Three treatments were disposed: control without sludge, and two treatments with 10 and 20 g sludge kg^?1, respectively. Control and the 10 g sludge kg^?1 treatments received NPK fertilizer to adjust the concentrations of major mineral nutrients to similar levels in all treatments. Soils were potted and planted with fenugreek. Plants harvested at the initial flowering stage were analysed for total Cr, Fe, Zn and Pb. Sequential soil extraction was applied to obtain operationally defined soil Cr fractions.

Results and discussion

Total Cr in all treatments was below or within the allowable range for agricultural soils (100–150 mg kg^?1). In control soils, most Cr was in the residual fraction (HF/HClO₄ digest). Tannery sludge-amended soils incorporated most Cr into the moderately reducible fraction (oxalic acid/ammonium oxalate extract). In fenugreek shoots, Cr concentrations reached 3.2 mg Cr kg^?1, a higher concentration than that reported for other leafy vegetables. Lead concentrations in plant shoots from this treatment were enhanced but hardly exceeded 1 mg Pb kg^?1.

Conclusions

Tannery sludge-amended soils containing Cr within the range of permissible concentrations can increase shoot Cr in fenugreek. Only sludge with low Pb concentrations should be used for Cr biofortification of fenugreek.     

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.     

An exploratory study of potential As and Pb contamination by atmospheric deposition in two urban vegetable gardens in Rome,Italy

Purpose

A preliminary study was carried out in Rome (Italy) to assess the potential role of atmospheric deposition in trace element contamination in urban vegetable gardens relative to human health risk from crop consumption.

Materials and methods

Two sites were selected on the basis of previously known contamination issues. Atmospheric deposition, parent material, soils properties affecting trace element mobility, and various anthropogenic inputs were considered. Soil samples were taken at depth from two points in each garden, within 5 cm of sampled crops. Inputs and crops were sampled and analysed for As and Pb content. A rain and dust gauge was set up in each garden for the duration of 93 days (late spring to late summer) for atmospheric deposition sampling.

Results and discussion

Atmospheric deposition influx was high at both sites (2.22 and 2.32 As and 2.67 and 3.42 Pb μg m^?3 day^?1). Soil pH was between 6.70 and 7.57 and texture varied from loamy sand to clay loam (3.4 to 31.9 % clay content). CEC ranged between 21.6 and 54.2 meq/100 g within rooting depth, rising almost commensurately with soil organic carbon (SOC) content (1.87–8.37 %). Somewhat high total soil Pb content (80.8–522.7 ppm) contrasted with negligible exchangeability and crop content (<0.01 ppm). Total soil As (17.0–32.0 ppm) corresponded with exchangeable and crop As for one site in one of the gardens. Leaves evinced high As accumulation levels (16.0–41.2 ppm) in all crops. High amounts of atmospheric Pb combined with negligible amounts of extractable Pb and Pb plant tissue content point to particulate inhalation and ingestion as a main health threat in the case of Pb. In contrast, food intake seems to be of greater concern relative to high As contamination. Greater soil As solubility may be explanatory, but the mostly low amounts of extractable As and the high atmospheric As suggest an airborne route being playing an important role.

Conclusions

Preliminary results suggest that research on trace element contamination in urban gardens should consider atmospheric deposition as a major contributing source.

     

The influence of compost addition on heavy metal distribution between operationally defined geochemical fractions and on metal accumulation in plant

Purpose

Metal distribution patterns among geochemical fractions are informative for metal phytoavailability. Compost added to polluted soils may adsorb metals on the less phytoavailable fractions. A bioassay experiment was conducted to establish possible correlations between metal concentrations in different soil fractions and metal contents in edible plant parts and to investigate the influence of different compost loads on heavy metal availability to plants.

Materials and methods

Chinese cabbage plants were grown in pots with sandy and clayey soils and soils mixed with different doses of biosolid compost spiked with soluble heavy metal salts (Cd, Cu, and Pb). The metals’ distribution pattern in the soil and mixed samples was determined by sequential extraction procedure (modified BCR protocol). The studied fractions, from most to least bioavailable, were water-extractable (WE), exchangeable-adsorbed (EXC), associated with carbonates and acetic acid-soluble forms (CARB), occluded by reducible (hydro)oxides of Fe and Mn (RO), and associated with organic matter (OM) and a residual fraction (RES). Metal concentrations in soil extracts and in the digested plant tissue were measured by ICP-AES.

Results and discussion

The highest compost doses (72 and 115 Mg ha^?1) enhanced cabbage yield significantly. No excessive phytoaccumulation of metals was observed in plants grown in the clayey soil or its mixtures with compost. The compost dose of 72 Mg ha^?1 was optimal in decreasing Cu accumulation by plants grown in sandy soil, and 28.8 Mg ha^?1 was found to be effective in reducing Cd and Pb uptake. Metals were accumulated in plants primarily from the WE, EXC, and CARB fractions, whereas other fractions decreased phytoaccumulation. Compost addition suppressed heavy metal mobility, but different fractions were active in pollutant sorption, depending on soil type and metal.

Conclusions

Compost addition increased metal proportions in the RO and OM fractions, reducing metal phytoavailability. This is especially important for sandy soils with low adsorption ability and higher vulnerability to metal pollution than clayey soils. A compost dose of 20% v/v (or 28.8 Mg ha^?1) effectively reduced plant accumulation of Cd and Pb. We propose using the first three steps of the modified BCR protocol as a three-step sequential-extraction procedure for the most phytoavailable fractions of heavy metal: WE, EXC, and CARB.     

Sampling soil and sediment depth profiles at a fine resolution with a new device for determining physical,chemical and biological properties: the Fine Increment Soil Collector (FISC)

Purpose

Many environmental investigations (empirical and modelling) and theories are based on reliable information on the depth distribution of physical, chemical and biological properties in soils and sediments. However, such depth profiles are not easy to determine using current approaches, and, consequently, new devices are needed that are able to sample soils and sediments at fine resolutions.

Materials and methods

We have designed an economic, portable, hand-operated surface soil/sediment sampler—the Fine Increment Soil Collector (FISC)—which allows for the close control of incremental soil/sediment sampling and for easy recovery of the material collected by a simple screw-thread extraction system. This innovative sampling system was developed originally for the beryllium-7 (⁷Be) approach in soil and sediment redistribution research. To ensure reliable estimates of soil erosion and sediment deposition from ⁷Be measurements, the depth distribution of this short-lived fallout radionuclide in soil/sediment at the resolution of millimetres is a crucial requirement. This major challenge of the ⁷Be approach can be met by using the FISC.

Results and discussion

We demonstrate the usefulness of the FISC by characterising the depth distribution of ⁷Be at increments of 2.5 mm for a soil reference site in Austria. The activity concentration of ⁷Be at the uppermost increment (0–2.5 mm) was ca. 14 Bq kg^?1 and displayed decreasing activity with depth. Using most conventional sampling devices (i.e. the scraper-plate system), the most accurate depth increment would have been 10 mm, and the activity concentration at the surface would have been considerably lower. Consequently, coarser sampling would have influenced estimates of ⁷Be-derived soil erosion and deposition. The potential application for other soil/sediment properties, such as nutrients (e.g. phosphorus), contaminants and carbon are also discussed.

Conclusions

By enabling soil and sediment profiles to be sampled at a depth resolution of millimetres, the FISC has the potential to provide key information when addressing several environmental and geoscientific issues, such as the precise depth distributions of soil/sediment nutrients, contaminants and biological properties.     

Spatial occurrence and geochemistry of soil salinity in Datong basin,northern China

Purpose

Soil quality assessment is tremendously important for agronomic and environmental concern. The objective of this study was to spatially evaluate soil salinity and its geochemistry at regional scale.

Materials and methods

A soil quality assessment study was conducted over a 1,000 km² field in Datong basin, northern China via collecting and determining 163 topsoil samples. A combined approach of statistical methods and hydrochemical tools was applied for a comprehensive analysis in this study.

Results and discussion

In the study area, the nonsaline lands (total dissolved solids (TDS) <0.08 %, Ca-HCO₃ type soils) that are located in the pluvial plains consist of coarse-medium sands and deep unsaturated zone (depth >10 m). The slightly (0.08 %?<?TDS?<?0.2 %, Ca-Na-HCO₃-NO₃ type soils) and the moderately (0.2 %?<?TDS?<?1 %, Ca-Na-SO₄ type soils) saline lands are located in the alluvial plains and the central basin composed of fine sediments like fine sands, loams and silts, and intermediately deep unsaturated zone (depth 2–10 m). By contrast, due to irrigation, the very (1 %?<?TDS?<?2 %) and the extremely (TDS >2 %) saline areas with Na-SO₄/Na-Cl type soils are locally found in some desolate lands comprised of silty clays and shallow unsaturated zone (depth <2 m) in the central basin.

Conclusions

As a result of water-rock/sediments interactions, effects of landscapes and anthropogenic activities, soil salinity is characterized by strong spatial variability in Datong. The new insights into the basin-scale distribution pattern of soil salinity in inland basins of silicate terrain under arid climatic conditions should be applicable in other similar regions of the world.     

The impact of different forest types on phytolith-occluded carbon accumulation in subtropical forest soils

Purpose

Occlusion of carbon in phytoliths is an important biogeochemical carbon sequestration mechanism and plays a significant role in the global biogeochemical carbon cycle and atmospheric carbon dioxide (CO₂) concentration regulation at a millennial scale. However, few studies have focused on the storage of phytolith and phytolith-occluded carbon (PhytOC) in subtropical forest soils.

Materials and methods

Soil profiles with 100-cm depth were sampled from subtropical bamboo forest, fir forest, and chestnut forest in China to investigate the variation of phytoliths and PhytOC storage in the soil profiles based on amass-balance assessment.

Results and discussion

The storage of phytoliths in the top 100 cm of the bamboo forest soil (198.13?±?25.08 t ha^?1) was much higher than that in the fir forest (146.76?±?4.53 t ha^?1) and chestnut forest (170.87?±?9.59 t ha^?1). Similarly, the storage of PhytOC in the bamboo forest soil (3.91?±?0.64 t ha^?1) was much higher than that in the fir forest soil (1.18?±?0.22 t ha^?1) and chestnut forest soil (2.67?±?0.23 t ha^?1). The PhytOC percentage in the soil organic carbon pool increased with soil depth and was the highest (4.29 %) in the bamboo forest soil. Our study demonstrated that PhytOC in soil was significantly influenced by forest type and the bamboo forest ecosystem contributed more significantly to phytolith carbon sequestration than other forest ecosystems.

Conclusions

Different forest types have a significant influence on the soil PhytOC storage. Optimization of bamboo afforestation/reforestation in future forest management plans may significantly enhance the biogeochemical carbon sink in the following centuries.

     

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

Purpose

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

Materials and methods

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

Results and discussion

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

Conclusions

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

     

Effect of lead pollution on soil microbiological index under spinach (Spinacia oleracea L.) cultivation

Purpose

Lead (Pb) pollution is appearing as an alarming threat nowadays in both developed and developing countries. Excessive Pb concentrations in agricultural soils result in minimizing the microbiological activities which leads to the decrease in crop production. A pot experiment was conducted with the purpose to examine the deleterious effect of Pb on microbiological index under spinach cultivation.

Materials and methods

Pb was added to 5 kg soil in each pot (with 6 seeds/pot) using Pb(NO₃)₂ at the rate of 0, 150, 300, 450, and 600 mg kg^?1 with three replications in completely randomized design. All soil microbial, enzymatic, and chemical properties and plant growth parameters and nutrient uptake were measured by standard methods.

Results and discussion

Both soil and plant measured parameters decreased after the addition of Pb (150, 300, 450, and 600 mg Pb kg^?1 soil) treatments with the passage of time (from 15 to 60 days) compared with control (CK). However, high Pb levels had more suppressive effect, therefore, highest Pb level (600 mg Pb kg^?1 soil) significantly (P?<?0.05) decreased the microbial biomass carbon (5.59-fold); microbial biomass nitrogen (N; 11.71-fold); microbial biomass phosphorus (P; 25.1-fold); dehydrogenase (4.02-fold); phosphatase (9.40-fold); urease (9.26-fold); pH (1.40-fold); spinach shoot (2.17-fold) and root (2.54-fold) length; shoot (2.36-fold) and root (2.69-fold) fresh weight; shoot (3.90-fold) and root (3.50-fold) dry weight; chlorophyll content (5.60-fold); carotenoid content (4.29-fold); plant macronutrients uptake, i.e., N (4.38- and 2.97-fold), P (3.88- and 6.58-fold), K (3.88- and 4.6-fold), Ca (6.60- and 6.70-fold), and Mg (5.57- and 4.45-fold); and plant micronutrient uptake, i.e., Zn (2.39- and 3.05-fold), Cu (3.70- and 2.62-fold), Fe (4.13- and 3.23-fold), and Mn (4.17- and 4.09-fold) in spinach shoot and root, respectively. Conversely, highest Pb level, i.e., 600 mg Pb kg^?1 soil significantly (P?<?0.05) increased the biomass carbon (C)/nitrogen (N) (4.69-fold) and C/P (6.01-fold) ratios, soil extractable Pb (5.87-fold), and Pb uptake in spinach shoot (3.58-fold) and root (4.38-fold), respectively, at the end of the experiment, i.e., day 60.

Conclusions

Pb contamination significantly decreased the soil microbial and enzymatic activities, pH, spinach plant growth, and nutrients uptake in all the samples spiked with Pb. The degree of the influence increased with the increased Pb concentrations and incubation time, showing that Pb threshold is strongly associated with the extent of Pb concentration and time to accumulate. The soil microbial biomass, enzymatic activities, pH, and spinach physiological indices, could be used as a sensitive indicators to reflect environmental stress in soil ecosystems.