Metabolic and bacterial diversity in soils historically contaminated by heavy metals and hydrocarbons

The aim of this study was to characterize soils contaminated by different levels of heavy metals and hydrocarbons (Madonna Dell'Acqua, Pisa, Italy). The soils were chemically and biochemically analysed by measuring the standard chemical properties and some enzyme activities related to microbial activity (dehydrogenase activity) and the soil carbon cycle (total and extracellular beta-glucosidase activities). The metabolic capacities of soil microorganisms to degrade hydrocarbons through catechol 2,3-dioxygenase were also described. The microbial diversity of contaminated and uncontaminated soils was estimated by denaturing gradient gel electrophoresis (DGGE) of amplified 16S rDNA sequences. The PCR/single-strand conformation polymorphism (PCR/SSCP) method was used to estimate the genetic diversity of PAH-degrading genes in both contaminated and uncontaminated soils. A greater bacterial diversity and lower catechol 2,3-dioxygenase activity was detected in unpolluted soils. The complexity of the microbial community (Shannon and Simpson indices) as well as the dehydrogenase soil activity negatively correlated with contamination levels. The greatest PAH-degrading gene diversity and the most intense catechol 2,3-dioxygenase activity were found in the soils with the highest levels of hydrocarbons. Heavy metals and hydrocarbon pollution has caused a genetic and metabolic alteration in microbial communities, corresponding to a reduction in microbial activity. A multi-technique approach combining traditional biochemical methods with molecular-based techniques, along with some methodological improvements, may represent an important tool to expand our knowledge of the role of microbial diversity in contaminated soil.     

Recycling of complexometric extractants to remediate a soil contaminated with heavy metals

Equilibrations were performed with complexing reagent(s) to mobilise Cd, Cu, Mn, Ni, Pb and Zn from a contaminated urban soil. The metal-laden aqueous extract was treated with zero-valent magnesium (Mg0) or bimetallic mixture (Pd0/Mg0 or Ag0/Mg0) to precipitate the heavy metals from solution while liberating the chelating reagent(s). Post precipitation, the pH of aqueous supernatant fraction was readjusted to approximately 5 and the solution was re-combined with the soil particulates to extract more heavy metal pollutants. A sparing quantity of EDTA (10 mmoles) mobilised 32-54% of the 5 mmoles of heavy-metals from the soil with three cycles but only 0.1% of the iron was removed. Three successive extractions with a mixture of complexing reagents (3 mmoles), 1:1 EDTA plus HEDC [bis-(2-hydroxyethyl)-dithiocarbamate], mobilised approximately 49% of the Pb, approximately 18% of the Zn and approximately 19% of the Mn burden but only 7% of the Cu, and 1% of the Fe from this soil. An appreciable fraction of the mobilised Pb and Cu and a portion of the Zn was cemented to the surfaces of the excess magnesium whereas virtually all of the Fe and Mn was removed from solution as insoluble hydroxides.     

EDTA-enhanced phytoremediation of contaminated calcareous soils: heavy metal bioavailability,extractability, and uptake by maize and sesbania

Natural and chemically enhanced phytoextraction potentials of maize (Zea mays L.) and sesbania (Sesbania aculeata Willd.) were explored by growing them on two soils contaminated with heavy metals. The soils, Gujranwala (fine, loamy, mixed, hyperthermic Udic Haplustalf) and Pacca (fine, mixed, hyperthermic Ustollic Camborthid), were amended with varying amounts of ethylenediaminetetraacetic acid (EDTA) chelating agent, at 0, 1.25, 2.5, and 5.0 mM kg^?1 soil to enhance metal solubility. The EDTA was applied in two split applications at 46 and 60 days after sowing (DAS). The plants were harvested at 75 DAS. Addition of EDTA significantly increased the lead (Pb) and cadmium (Cd) concentrations in roots and shoots, uptake, bioconcentration factor, and phytoextraction rate over the control. Furthermore, addition of EDTA also significantly increased the soluble fractions of Pb and Cd in soil over the controls; the maximum increase of Pb and Cd was 13.1-fold and 3.1-fold, respectively, with addition of 5.0 mM EDTA kg^?1soil. Similarly, the maximum Pb and Cd root and shoot concentrations, translocation, bioconcentration, and phytoextraction efficiency were observed at 5.0 mM EDTA kg^?1 soil. The results suggest that both crops can successfully be used for phytoremediation of metal-contaminated calcareous soils.     

Monitoring and assessment of toxic metals in Gulf War oil spill contaminated soil using laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) was applied for the detection of toxic metals in oil spill contaminated soil (OSCS). The OSCS samples were collected from Khursania Saudi Arabia along the coast of Persian Gulf exposed to oil spills in 1991 Gulf war. Environmentally important elements like Aluminum Magnesium, Calcium, Chromium, Titanium, Strontium, Iron, Barium, Sodium, potassium, Zirconium and Vanadium from the contaminated soil have been detected. Optimal experimental conditions for analysis were investigated. The LIBS system was calibrated using standard samples containing these trace elements. The results obtained using Laser-Induced Breakdown Spectroscopy (LIBS) were compared with the results obtained using Inductively Coupled Plasma Emission Spectroscopy (ICP). The concentrations of some elements (Ba and Cr) were found higher than permissible safe limits. Health risks associated with exposure to such toxic elements are also discussed.     

Accumulation of Cu, Cd, Cr, Mn and Pb from artificially contaminated soil by Bacopa Monnieri

The metal accumulation potential of Bacopa monnieri L. was assessed under simulated laboratory conditions. This study was carried out in mixed metals (Cu, Cd, Pb, Cr, Mn) condition and repeated exposures in artificial contaminated soil. The growing shoots were planted in garden subsoil containing 3, 16, 32, 64, 160 M each of the above metals. After 8 weeks, plants were refeeded to three times higher concentrations of each metal than initially used to assess the maximum accumulating potential of the metals. The accumulation of the metals by the root and shoot was concentration and duration dependent. The metal accumulation was considerably higher in the fine root than in the shoot and showed the following order : Mn > Cr > Cu > Cd > Pb. The plants showed high tolerance to the metals as no visible phytotoxic symptom was produced after 8 weeks. However, as a result of combined metal toxicity, chlorophyll content was reduced by 62% after 12 weeks. The highest metal concentration was lethal to the plant at 16 weeks. In view of their high tolerance, the plants of B. monnieri may be considered for the amelioration of industrially-polluted wetlands experiencing regular flushing of wastewaters.     

Mercury uptake and allocation in Juncus maritimus: implications for phytoremediation and restoration of a mercury contaminated salt marsh

Juncus maritimus is the most abundant macrophyte in Laranjo bay, a Portuguese salt marsh heavily polluted by mercury (Hg). With the aim to elucidate the role of this species in the salt marsh Hg cycling and restoration, plants were harvested between March 2006 and January 2008 from four locations differing in Hg contamination. Metal uptake and distribution between plant organs were evaluated, biomass and Hg pools were also determined. Results showed that J. maritimus may influence the sediment pH and Eh, thus increasing the Hg available for uptake. Most (95-98%) of the absorbed Hg was retained belowground, phytostabilizing the metal and reducing the amount of Hg in the sediments. These results suggest that in salt marshes dominated by J. maritimus the approach could be phytostabilization, where these plants can be used to immobilize metals and store them belowground, reducing the pool of bioavailable Hg within contaminated marshes and acting as a sink rather than a source of contamination to the surrounding areas.     

In situ laser-induced fluorescence (LIF) analysis of petroleum product-contaminated soil samples

General considerations of the calibrations of in situ measurements are presented and the concept of using an "average oil" with average analysability for calibration purposes is introduced. The in situ analysis of 30 petroleum product-contaminated soil samples with laser-induced fluorescence (LIF) spectroscopy was performed. Compared to an uncontaminated laboratory reference (LR) soil, 23 soil samples exhibited significantly higher LIF signals, so that these soil samples were classified as contaminated. The repeatability and reproducibility of the in situ LIF analysis were investigated. For the calibration of the LIF data, two LR oils (a fuel oil and a crude oil) were employed. The degree of soil contamination with petroleum products ranged from the limit of detection (LOD) for LIF analysis (ca. 100 ppm), or below, to more than 10,000 ppm. The petroleum product concentrations determined with in situ LIF analysis reveal a reasonable correlation with the results of standard IR analysis after extraction of the contaminated soils.     

Microbiological characteristics of multi-media PRB reactor in the bioremediation of groundwater contaminated by petroleum hydrocarbons

A multi-media bio-PRB reactor was designed to treat groundwater contaminated with petroleum hydrocarbons. After a 208-day bioremediation, combined with the total petroleum hydrocarbons content in the groundwater flowed through the reactor, microbiological characteristics of the PRB reactor including microbes immobilized and its dehydrogenase activity were investigated. TPH was significantly reduced by as much as 65% in the back of the second media layer, whereas in the third layer, the TPH content reached lower than 1 mg l?1. For microbes immobilized on the media, the variations with depth in different media were significantly the same and the regularity was obvious in the forepart of the media, which increased with depth at first and then reduced gradually, while in the back-end, the microbes almost did not have any variations with depth but decreased with the distance. The dehydrogenase activity varied from 2.98 to 16.16 mg TF L?1 h?1 and its distribution illustrated a similar trend with numbers of microbial cell, therefore, the noticeable correlation was found between them.     

Uptake and bioavailability of persistent organic pollutants by plants grown in contaminated soil

This paper assesses the uptake of persistent organic pollutants (POP's) into plants. In particular, uptake of alpha-endosulfan, beta-endosulfan and endosulfan sulfate from lettuce. The lettuce plants were grown on compost that had previously been contaminated at 10 and 50 microg g(-1) per POP. The soil was slurry spiked by adding the appropriate amount of POP in acetone in an approximate ratio of 1 ratio 2, w/v soil ratio solvent. The solvent was left to evaporate at ambient temperature for 24 hours. Lettuce plants were grown under artificial daylight for 12 hours a day. The influence of soil ageing on the recovery of POP's from spiked soil samples was also assessed. The average recovery of endosulfan compounds from slurry spiked soil (10, 20 and 40 microg g(-1)) was consistent (92.9 +/- 4.4% for n= 9). However, ageing of endosulfan compounds on the slurry spiked soil resulted in lower recoveries (average losses were 12.5% after 14 days ageing of slurry spiked soil). The uptake of POP's was assessed by measuring the amount of endosulfan compounds in roots and leaves from lettuce plants after 10, 20 and 33 days. In addition, control plants grown in uncontaminated soil were monitored and analysed. It was found that endosulfan compounds were present in the roots of all lettuce plants irrespective of soil spike level or age of plant. In the 33 day lettuce plants where the soil was spiked at the highest level (50 microg g(-1)) endosulfan compounds were determined in the leaves. The root to leaf ratio was found to be 3.1 for alpha-endosulfan, 46.0 for beta-endosulfan, and 24.3 for endosulfan sulfate. Spiked lettuce samples were subjected to in vitro gastrointestinal extraction to assess the bioavailability of endosulfan compounds. No detectable endosulfan compounds were determined in the gastric extracts while small quantities (range 0.06-0.12 microg g(-1)) were found in the intestinal extraction. All samples (soil and lettuce) were extracted using pressurised fluid extraction and analysed using gas chromatography with mass selective detection.     

顶空气相色谱质谱法测定土壤中挥发性卤代烃方法研究

采用顶空气相色谱质谱法(HS/GC-MS)对土壤中挥发性卤代烃进行了测定,优化了分析的顶空条件、气相色谱质谱分离条件。在优化条件下成功实现了24种挥发性卤代烃的分离,确定了分析方法的检出限、测定下限、精密度及回收率等质量控制参数。方法的检出限为0.8~4.4μg/kg,测定下限为3.2~17.6μg/kg。当加标量为100μg/kg和250μg/kg时,相对标准偏差分别为1.3%~12.6%和2.6%~8.7%,加标回收率分别为71.4%~126%和63.1%~121%。     

Metal immobilization and phosphorus leaching after stabilization of pyrite ash contaminated soil by phosphate amendments

In this study we would like to show the importance of a holistic approach to evaluation of chemical stabilization using phosphate amendments. An extensive evaluation of metal stabilization in contaminated soil and an evaluation of the leaching of phosphorus induced after treatment were performed. The soil was highly contaminated with Cu (2894 mg kg(-1)), Zn (3884 mg kg(-1)), As (247 mg kg(-1)), Cd (12.6 mg kg(-1)) and Pb (3154 mg kg(-1)). To immobilize the metals, mixtures of soil with phosphate (from H(3)PO(4) and hydroxyapatite (HA) with varying ratios) were prepared with a constant Pb : P molar ratio of 1: 10. The acetic acid extractable concentration of Pb in the mixture with the highest amount of added phosphoric acid (n(H(3)PO(4)) : n(HA) = 3 : 1) was reduced to 1.9% (0.62 mg L(-1)) of the extractable Pb concentration in the untreated soil, but the content of water extractable phosphorus in the samples increased from 0.04 mg L(-1) in the untreated soil sample up to 14.3 mg L(-1) in the same n(H(3)PO(4)) : n(HA) = 3 : 1 mixture. The high increase in arsenic mobility was also observed after phosphate addition. The PBET test showed phosphate induced reduction in Pb bioavailability. In attempting to stabilize Pb in the soil with the minimum treatment-induced leaching of phosphorus, it was found that a mixture of soil with phosphate addition in the molar ratio of H(3)PO(4) : HA of 0.75 : 1 showed the most promising results, with an acetic acid extractable Pb concentration of 1.35 mg L(-1) and a water extractable phosphorus concentration of 1.76 mg L(-1). The time-dependent leaching characteristics of metals and phosphorus for this mixture were evaluated by a column experiment, where irrigation of the soil mixture with the average annual amount of precipitation in Slovenia (1000 mm) was simulated. The phosphorus concentration in the leachates decreased from 2.60 mg L(-1) at the beginning of irrigation to 1.00 mg L(-1) at the end.     

Impact of sewage contaminated water on soil, vegetables, and underground water of peri-urban Peshawar, Pakistan

The use of sewage-contaminated municipal water for irrigation of crops is an old practice in many big cities of Pakistan. Since the wastewater is rich in nutrients, it increases crops yield substantially but at the cost of food quality. The objective of this study was to investigate sewage water irrigation as a source of accumulation of heavy metals in soil and its subsequent transfer to crops and underground water. Sewage water, soil, groundwater, and crop samples were collected from selected areas around Peshawar city and analyzed for heavy metals concentration by atomic absorption spectroscopic method. Analysis of data revealed a considerable impact of the irrigation practices in the peri-urban Peshawar. Statistical analysis of the data showed a positive correlation between heavy metals concentration and soil carbon contents on the one hand and cation exchange capacity on the other. A strongly negative correlation was observed between metal contents and soil pH. The vertical movement of heavy metals from contaminated soil has polluted crops and underground water. The results indicated higher concentration of toxic metals in soil accumulated due to long-term sewage-contaminated water irrigation and their subsequent transfer to our food chain. The practice, if continued un-noticed may pose a threat of phytotoxicity to the local population.     

高密度电法在原位修复土壤过程中的监控研究

采用高密度电阻率成像法（ERT）对上海市某有机污染场地土壤污染原地修复进行研究，通过持续监测药剂注入前后电阻率的改变来推断药剂和污染物的扩散路径。结果表明，药剂扩散的影响半径介于2 m～4 m之间；其影响深度根据注药点和土壤渗透性差异而有所不同，在16 m处注药的影响深度大于监测深度20 m，ERT技术在监控原位注入修复过程中具有较好的可行性和适用性。     

Polycyclic aromatic hydrocarbons in water, sediment and soil of the Songhua River Basin, China

The Songhua River is the third largest river in China and the primary source of drinking and irrigation water for northeastern China. The distribution of 16 priority polycyclic aromatic hydrocarbons (PAHs) in water [dissolved water (DW) and suspended particulate matter (SPM)], sediment, and soil in the river basin was investigated, and the associated risk of cancer from these PAHs was also assessed. The total concentration of PAHs ranged from 13.9 to 161 ng L^?1 in DW, 9.21 to 83.1 ng L^?1 in SPM, 20.5 to 632 ng g^?1 dw (dry weight) in sediment, and from 30.1 to 870 ng g^?1 dw in soil. The compositional pattern of PAHs indicated that three-ring PAHs were predominant in DW and SPM samples, while four-ring PAHs dominated in sediment and soil samples. The spatial distribution of PAHs revealed some site-specific sources along the river, with principal component analysis indicating that these were from pyrogenic sources (such as coal and biomass combustion, and vehicle emissions) and coke oven emission distinguished as the main source of PAHs in the Songhua River Basin. Based on the ingestion of PAH-contaminated drinking water from the Songhua River, cancer risk was quantitatively estimated by combining the Incremental Lifetime Cancer Risk assessment model and BaP-equivalent concentration for five age groups of people (adults, teenagers, children, toddlers, and infants). Overall, the results suggest that the estimated integrated lifetime cancer risk for all groups was in acceptable levels. This study is the first attempt to provide information on the cancer risk of PAHs in drinking water from the Songhua River.     

Effects of selected soil properties on phytoremediation applicability for heavy-metal-contaminated soils in the Apulia region, Southern Italy

Phytoremediation is a well-known promising alternative to conventional approaches used for the remediation of diffused and moderated contaminated soils. The evaluation of the accumulation, availability, and interactions of heavy metals in soil is a priority objective for the possible use of phytoremediation techniques such as phytoextraction and phytostabilization. The soils used in this work were collected from a number of sites inside a protected area in the Apulia region (Southern Italy), which were contaminated by various heavy metals originated from the disposal of wastes of different sources of origin. Soils examined contained Cd, Cr, Cu, Ni, Pb, and Zn in amounts exceeding the critical limits imposed by EU and Italian laws. However, the alkaline conditions, high organic matter content, and silty to silty loamy texture of soils examined would suggest a reduced availability of heavy metals to plants. Due to the high total content but the low available fraction of heavy metals analyzed, especially Cr, phytoextraction appears not to be a promising remediation approach in the sites examined, whereas phytostabilization appears to be the best technique for metal decontamination in the studied areas.     

Preliminary studies of a fast screening method for polycyclic aromatic hydrocarbons in soil by using solvent microextraction-gas chromatography

Solvent microextraction (SME) was applied to the extraction of polycyclic aromatic hydrocarbons (PAHs) from spiked and real environmental soil samples with different matrices. Soil sample was mixed with 7 mL of acetone and 14 mL of water to allow partitioning of the PAHs from the soil to the liquid phase. A 2 microL octane drop suspended from a microsyringe needle tip was then immersed into the stirred solution-soil mixture for extraction. After an 11 min extraction, the octane drop was withdrawn into the syringe and injected directly into the GC for identification and quantification. The whole analysis procedure took 27 min, with an extraction time of 11 min, and a GC separation time of 16 min. A second extraction could be undertaken whilst the GC is running, hence the GC run time currently limits the sample throughput. In this method, a small amount of organic solvent was used for the extraction process, which produced little waste. The limits of detection for lower molecular weight (< 230) PAHs range from 0.13 to 0.36 mg kg-1, and for higher molecular weight (> 250) PAHs are estimated to be between 0.5 and 1.0 mg kg-1, with RSD values generally under 20%. Due to the small volumes of organic solvent used, the consumable cost per extraction is only US$ 0.12. This is the first report of the application of SME to solid samples, and the first report of the use of SME for the analysis of PAHs.     

Contamination, source identification, and risk assessment of polycyclic aromatic hydrocarbons in agricultural soil of Shanghai, China

The level, distribution, compositional pattern, and possible sources of polycyclic aromatic hydrocarbons (PAHs) in agricultural soil of Shanghai were investigated. The concentrations ranged from 140.7 to 2,370.8 μg kg(?-1) for 21 PAHs and from 92.2 to 2,062.7 μg kg(?-1) for 16 priority PAHs, respectively. The higher level of PAHs was mainly distributed in the south and west of Shanghai region, and the lower concentration was found in Chongming Island. Generally, the composition pattern of PAHs was characterized with high molecular weight PAHs, the seven possible carcinogenic PAHs accounted for 4.8-50.8% of the total PAHs, and fluoranthene, pyrene, and benzo[b]fluoranthene were the most dominant components in soil samples. The correlation analysis suggested that low molecular weight PAHs and high molecular weight PAHs were originated from different sources and further corroborated that total organic carbon was a key soil property affecting the fate of persistent organic pollutants in the environment. The isomer ratios and principal component analysis indicated that PAHs in the investigated areas were derived primarily from combustion of biomass, coal, and petroleum. Compared to the soil quality standards of the Netherlands, all the target PAHs (except Ant) in most samples exceeded their target values. The Nemerow composite index based on the same soil quality standard showed that 69.4% of the soil samples were heavily polluted. The total BaP(eq) of ten Dutch target PAHs in 72% soil samples were higher than the reference total carcinogenic potency. Therefore, the agricultural soil in Shanghai is suffering from serious PAHs contamination.