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.     

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.     

混合溶剂解吸土壤中多环芳烃的研究

对比了水溶性有机溶剂乙醇、正丙醇、丙酮、已戊醇和水对土壤中多环芳烃(PAHs)的解吸效果,结果综合实验效果、安全性和经济等因素,主要采用了乙醇和戊醇作为混合试剂的主要成分。对比了乙醇、戊醇和水不同配比的混合试剂对土壤的解吸效果,最终选用混合试剂(5%戊醇+20%水+75%乙醇)研究污染土壤中PAHs的解吸行为,分别进行了解吸动力实验、分阶段解吸实验和pH值影响实验。结果表明,土壤中PAHs的解吸是一个快速反应,5h基本达到解吸平衡,高环物质(4～6环PAHs)比低环物质(2～3环PAHs)的解吸速率慢。分步解吸率表明,随着环数的增加,第一步解吸率逐渐降低,第二、三步的解吸率则逐渐增大,第二、三步的解吸作用对高环PAHs更为明显。pH值对混合溶剂解吸土壤中PAHs有显著影响,pH值在5 5～7之间时,对土壤中PAHs的解吸影响最明显,碱性环境(pH>7)有利于土壤中PAHs的解吸,酸性环境则不利于解吸实验的进行。     

Comparison of soil solution sampling techniques to assess metal fluxes from contaminated soil to groundwater

The unsaturated zone plays a major role in elemental fluxes in terrestrial ecosystems. A representative chemical analysis of soil pore water is required for the interpretation of soil chemical phenomena and particularly to assess Trace Elements (TEs) mobility. This requires an optimal sampling system to avoid modification of the extracted soil water chemistry and allow for an accurate estimation of solute fluxes. In this paper, the chemical composition of soil solutions sampled by Rhizon® samplers connected to a standard syringe was compared to two other types of suction probes (Rhizon®?+?vacuum tube and Rhizon®?+?diverted flow system). We investigated the effects of different vacuum application procedures on concentrations of spiked elements (Cr, As, Zn) mixed as powder into the first 20 cm of 100-cm columns and non-spiked elements (Ca, Na, Mg) concentrations in two types of columns (SiO₂ sand and a mixture of kaolinite?+?SiO₂ sand substrates). Rhizon® was installed at different depths. The metals concentrations showed that (i) in sand, peak concentrations cannot be correctly sampled, thus the flux cannot be estimated, and the errors can easily reach a factor 2; (ii) in sand?+?clay columns, peak concentrations were larger, indicating that they could be sampled but, due to sorption on clay, it was not possible to compare fluxes at different depths. The different samplers tested were not able to reflect the elemental flux to groundwater and, although the Rhizon®?+?syringe device was more accurate, the best solution remains to be the use of a lysimeter, whose bottom is kept continuously at a suction close to the one existing in the soil.     

Evaluation of electrochemical processes for the removal of several target aromatic hydrocarbons from petroleum contaminated water

Ground and surface water contamination resulting from the leakage of crude oil and refined petroleum products is a serious and growing environmental problem throughout the world. Consequently, a study of the use of electrochemical treatment in the clean-up was undertaken with the aim of reducing the water contamination by aromatic pollutants to more acceptable levels. In the experiments described, water contamination by refined petroleum products was simulated under laboratory conditions. Electrochemical treatment, using aluminium electrodes, has been optimised by full factorial design and surface response analysis in term of BTEX and PAHs removal and energy consumption. The optimal conditions of pH, current density, electrolysis time, electrolyte type, and electrolyte concentration have then been applied in the treatment of real water samples which were monitored as petroleum contaminated samples. Treatment results have shown that electrochemical methods could achieve the concentration of these pollutants to undetectable levels in particular groundwater and surface water, hence, they can be highly effective in the remediation of water contaminated by aromatic hydrocarbons, and the use of these processes is therefore recommended.     

Mutagenicity assessment of contaminated soil in the vicinity of industrial area

In the industrial area of Chinhat, Lucknow (India) wastewater coming from pesticide manufacturing and other industries is used to irrigate the agricultural crops. This practice has been polluting the soil and pollutants might reach the food chain. Gas chromatographic analysis revealed the presence of certain organochlorine pesticides in soil samples. Samples were extracted using different solvents, i.e., hexane, acetonitrile, methanol, chloroform, and acetone (all were HPLC-grade, SRL, India). Soil extracts were assayed for mutagenicity using Ames Salmonella/mammalian microsome test. Mutagenicity was observed in the test samples and TA98 was the most responsive strain for all the soil extracts (irrigated with wastewater) in terms of mutagenic index in the presence (+S9) and absence (−S9) of metabolic activation. In terms of slope (m) of linear dose–response curve for the most responsive strain TA98 exhibited highest sensitivity against the soil extracts in the presence and absence of S9 fraction. Hexane-extracted soil sample (wastewater) exhibited maximum mutagenicity in terms of net revertants per gram of soil in the presence and absence of S9 mix as compared to the other soil extracts. Groundwater-irrigated soil extracts displayed low level of mutagenicity as compared to wastewater-irrigated soil. The soil is accumulating a large number of pollutants due to wastewater irrigation and this practice of accumulation has an adverse impact on soil health.     

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.     

红外光度法测定土壤中的石油类

以CCl4为萃取剂,以Na2SO4(无水硫酸钠)或一水合硫酸镁MgSO4·H2O为干燥剂,用红外光度法(GB/T16488-1996)来测定土壤中的石油类。     

Remediation aspect of microbial changes of plant rhizosphere in mercury contaminated soil

Phytoremediation, an approach that uses plants to remediate contaminated soil through degradation, stabilization or accumulation, may provide an efficient solution to some mercury contamination problems. This paper presents growth chamber experiments that tested the ability of plant species to stabilize mercury in soil. Several indigenous herbaceous species and Salix viminalis were grown in soil collected from a mercury-contaminated site in southern Poland. The uptake and distribution of mercury by these plants were investigated, and the growth and vitality of the plants through a part of one vegetative cycle were assessed. The highest concentrations of mercury were found at the roots, but translocation to the aerial part also occurred. Most of the plant species tested displayed good growth on mercury contaminated soil and sustained a rich microbial population in the rhizosphere. The microbial populations of root-free soil and rhizosphere soil from all species were also examined. An inverse correlation between the number of sulfur amino acid decomposing bacteria and root mercury content was observed. These results indicate the potential for using some species of plants to treat mercury contaminated soil through stabilization rather than extraction. The present investigation proposes a practical cost-effective temporary solution for phytostabilization of soil with moderate mercury contamination as well as the basis for plant selection.     

An assessment of the bioavailability of persistent organic pollutants from contaminated soil

A procedure to assess the bioavailability of persistent organic pollutants (POPs) from soil samples has been developed. The procedure is based on the use of simulated in vitro gastrointestinal extraction to remove POPs from soil matrices. The level of recovery, using this approach, is assessed following liquid-liquid extraction (LLE) and analysis by gas chromatography-mass selective detection (GC-MSD). The remaining soil residue is then extracted using pressurised fluid extraction (PFE) followed by GC-MSD analysis to assess the residual fraction. The residual fraction is monitored to determine the unavailable fraction i.e. not available for absorption in the gastrointestinal tract of humans. The procedure was applied to four soil samples i.e. an aged, spiked soil and three certified reference materials (CRMs) contaminated with POPs. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II), phenols (cresol, TCP and PCP), and base neutral compounds (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from aged, spiked soil following extraction with gastric fluid ranged from 0.8 to 8.3% while following intestinal extraction ranged from 5.5 to 13.5%, irrespective of POP. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II) from CRM 805-050 following extraction with gastric fluid were below the limit of detection while following intestinal extraction ranged from 5.3 to 12.8%. Recoveries of phenols (cresol, TCP and PCP) from CRM 401-225 following extraction with gastric fluid ranged from 1.6 to 2.0% while following intestinal extraction ranged from 4.1 to 5.4%. Recoveries of base neutral acid analytes (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from CRM 107-100 following extraction with gastric fluid ranged from 1.4 to 4.0% while following intestinal extraction ranged from 6.6 to 12.7%. It has been found that the majority of POPs present i.e. >75%, would be excreted if consumed and not be absorbed in the gastrointestinal tract of humans.     

In situ phytoremediation of a soil historically contaminated by metals, hydrocarbons and polychlorobiphenyls

In the past several years, industrial and agricultural activities have led to serious environmental pollution, resulting in a large number of contaminated sites. As a result, much recent research activity has focused on the application of bioremediation technologies as an environmentally friendly and economically feasible means for decontamination of polluted soil. In this study horse manure and Populus nigra (var. italica) (HM + P treatment) have been used, at real scale level, as an approach for bioremediation of a soil historically contaminated by metals (Pb, Cr, Cd, Zn, Cu and Ni) and organic contaminants, such as polychlorobiphenyls and petroleum hydrocarbon. After one year, the HM + P phytotreatment was effective in the reclamation of the polluted soil from both organic and inorganic contaminants. A reduction of about 80% in total petroleum hydrocarbon (TPH), and 60% in polychlorobiphenyls (PCBs) and total metals was observed in the HM + P treatment. In contrast, in the horse manure (HM) treatment, used as control, a reduction of only about 30% of TPH was obtained. In order to assess both effectiveness and evolution of the remediation system to a biologically active soil ecosystem, together with the pollution parameters, the parameters describing the evolution of the soil functionality (enzymatic activities and protein SDS-PAGE pattern) were investigated. A stimulation of the metabolic soil processes (increase in dehydrogenase activity) was observed in the HM + P compared to the HM treatment. Finally, preliminary protein SDS-PAGE results have permitted the identification of proteins that have been recovered in the HM + P soil with respect to the HM; this may become a basic tool for improving the biogeochemical status of soil during the decontamination through the identification of microbial populations that are active in soil decontamination.     

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.     

A novel sensor for monitoring leakage of petroleum and other liquid hydrocarbons into soil environments

This paper describes the use of a potentially implantable infrared reflectometer for the qualitative detection of petroleum and a number of other hydrocarbon solvents. A rugged, low-power, re-useable sensor was evaluated in the laboratory for its ability to detect petrol in soil. A hydrophobic fluoropolymer was used as the sensing surface due to its high selectivity for petroleum hydrocarbons. The photocurrent reflected by this surface from a near IR source was measured to test for petroleum saturation within the membrane, which in turn was an indicator of petroleum in the surrounding soil. The simplicity in the sensor design enabled a stable, low cost detection method for petroleum and other hydrocarbons, ideal for use in sub-surface applications.     

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.     

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.     

Monitoring the effects of chelating agents and electrical fields on active forms of Pb and Zn in contaminated soil

The application of electrical fields and chelating agents is an innovative hybrid technology used for the decontamination of soil polluted by heavy metals. The effects of four center-oriented electrical fields and chelating agents on active fractions of lead and zinc were investigated in this pot experiment. Ethylenediaminetetraacetic acid (EDTA) as a synthetic chelator and cow manure extract (CME) and poultry manure extract (PME) as natural chelators were applied to the pots (2 g kg^?1) 30 days after the first irrigation. Two weeks later, four center-oriented electrical fields were applied in each pot (in three levels of 0, 10, and 30 V) for 1 h each day for 14 days. The soil near the cathode and anodes was collected and analyzed as cathodic and anodic soil, respectively. Results indicated that the soluble–exchangeable fraction of lead and zinc were decreased in the cathodic soil, while the carbonate-bound fractions were increased. In the anodic soil, however, the opposite result was observed. EDTA enhanced the soluble–exchangeable form of the metals in both anodic and cathodic soils. Furthermore, the amounts of carbonate-bound heavy metals were increased by the application of CME in both soils. The organic-bound fraction of the metals was increased by the application of natural chelators, while electrical fields had no significant impacts on this fraction.     

Monitoring of soil and groundwater contamination following a pipeline explosion and petroleum product spillage in Ijegun, Lagos Nigeria

In May 2008, an accidental damage of a Nigerian National Petroleum Corporation (NNPC) pipeline occurred in Ijegun area of Lagos, Nigeria, resulting in oil spillage and consequent contamination of the environment. The residual concentration of the total hydrocarbon (THC) and benzene, toluene, ethylbenzene, and xylene (BTEX) in the groundwater and soil was therefore investigated between March 2009 and July 2010. Results showed elevated THC mean levels in groundwater which were above the World Health Organization maximum admissible value of 0.1 mg/l. THC values as high as 757.97 mg/l in groundwater and 402.52 mg/l in soil were observed in March 2009. Pronounced seasonal variation in the concentration of THC in groundwater and soil samples show that there was significant (P?<?0.05) difference in the measured concentration of THC between each season (dry and wet), with the highest being in the dry season and between the years 2009 and 2010. Significant hydrocarbon contamination, 500 m beyond the explosion site and 25 months after the incident, was observed revealing the extent of the spillage of petroleum products. The highest concentrations of 16.65 μg/l (benzene), 2.08 μg/l (toluene), and 4864.79 μg/l (xylene) were found in stations within the 100 m buffer zone. Most of the samples of groundwater taken were above the target value of 0.2 μg/l set for BTEX compounds by the Environmental Guidelines and Standards for Petroleum Industry in Nigeria. The level of hydrocarbon in the impacted area calls for concern and remediation of the area is urgently needed to reduce further negative impact on the ecosystem.     

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.     

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.