Earthworm assisted bioremediation of organic contaminants

Due to their biological, chemical and physical actions, earthworms can be directly employed within bioremediation strategies to promote biodegradation of organic contaminants. Earthworms have been shown to aerate and bioturbate soils and improve their nutritional status and fertility, which are variables known to limit bioremediation. Earthworms have also been shown to retard the binding of organic contaminants to soils, release previously soil-bound contaminants for subsequent degradation, and promote and disperse organic contaminant degrading microorganisms. This review discusses these earthworm actions upon the soil environment and how they might influence the fate and behaviour of soil associated organic contaminants, subsequently improving bioremediation potential. The latter part of this review considers organic compounds in the following order: agrochemicals, petroleum and crude oil hydrocarbons, PAHs and PCBs.     

The Challenges and Solutions for Cadmium-contaminated Rice in China: A Critical Review

The wide occurrence of Cd-contaminated rice in southern China poses significant public health risk and deserves immediate action, which arises primarily from extensive metal (including Cd) contamination of paddies with the fast expansion of nonferrous metal mining and smelting activities. Accumulation of Cd in rice grains can be reduced by removing Cd from the contaminated paddy soils, reducing its bioavailability, and controlling its uptake by rice plants. Although a range of measures can be taken to rehabilitate Cd-contaminated lands, including soil replacement and turnover, chemical washing, and phytoremediation, they are either too expensive and/or too slow. Various amendment materials, including lime, animal manures, and biochar, can be used to immobilize Cd in soils, but such fixation approach can only temporarily reduce Cd availability to rice uptake. Cultivation of alternative crops with low Cd accumulation in edible plant parts is impractical on large scales due to extensive contamination and food security concerns in southern China. Transgenic techniques can help develop rice cultivars with low Cd accumulation in grains, but little public acceptance is expected for such products. As an alternative, selection and development of low-Cd rice varieties and hybrids through plant biotechnology and breeding, particularly, by integration of marker-assisted selection (MAS) with traditional breeding, could be a practical and acceptable option that would allow continued rice production in soils with high bioavailability of Cd. Plant biotechnology and breeding can also help develop Cd-hyperaccumulating rice varieties, which can greatly facilitate phytoremediation of contaminated paddies. To eliminate the long-term risk of Cd entering the food chain, soils contaminated by Cd should be cleaned up when cost-effective remediation measures are available.     

Determination of total petroleum hydrocarbons and heavy metals in soils within the vicinity of facilities handling refined petroleum products in Lagos metropolis

This article discusses the determination of total petroleum hydrocarbons (TPH) and heavy-metal contamination in soils within areas of refined petroleum products handling in Lagos metropolis. Soil samples were collected randomly from two petrol stations, two auto-mechanic workshops, and a National Electric Power Authority (NEPA) station. Control samples were taken from two low-density residential areas. TPH were estimated gravimetrically following standard methods of TPH analysis, while the heavy metals were determined by atomic absorption spectrophotometry. Sites studied had higher levels of TPH and heavy metals compared to the control samples. For TPH, the petrol stations have mean values of 399.83+/-106.19 and 450.83 +/- 90.58 microg/g, respectively; mechanic workshops, 362.60 +/- 185.84 and 428.55 +/- 119.00 microg/g, respectively; while the NEPA station has 356.20 +/- 210.30 microg/g compared to the control mean of 26.63 +/- 4.58. It revealed that the improper handling of refined petroleum products are potential sources of soil contamination in the sampled sites. This is indicated by the statistically significant levels of TPH and heavy metals observed between the control samples and those collected from the petroleum products handling sites. Bioremediation using microorganisms and plants is recommended.     

The co-application of earthworms (Dendrobaena veneta) and compost to increase hydrocarbon losses from diesel contaminated soils

The feasibility of using composted civic waste for the remediation of a soil contaminated with petroleum hydrocarbons (extractable petroleum hydrocarbons (EPH) 10+/-1.8 g kg(-1) and total 16 USEPA PAH 1.62+/-0.5 g kg(-1)) was assessed. The effects of compost to soil ratio, in combination with and without earthworm presence (Dendrobaena veneta), upon the loss of contaminants were determined for EPH (GC-FID) and PAH (GC-MS), respectively. Increasing the ratio of compost substrate to hydrocarbon impacted soil (1:0.5, 1:1, 1:2 and 1:4 (soil:compost wt/wt)) in the absence of earthworms resulted in significantly (p<0.05) greater losses of both EPH and SigmaPAH after an 84 d incubation period, when compared to the soil only control. Where earthworms were present without compost, EPH losses were significantly (p<0.05) enhanced in the soil only treatment (33.4+/-5.3% residual) compared to the soil only control (54.4+/-5.3% residual). However, PAH loss in the soil only treatment (with-earthworm presence) were only slightly enhanced (65.3+/-9.3% residual), with respect to the soil only control (69.2+/-6.4% residual). Synergistic benefits of both earthworm and compost presence were most significant for PAHs (p<0.05), and less so for EPH. (14)C-respirometer studies, to establish catabolic competence in terms of microbial mineralisation of key hydrocarbons, complemented the hydrocarbon analysis.     

Inputs and fates of petroleum hydrocarbons in a subtropical marine estuary

Inputs and fates of petroleum from a higly urbanized area to a subtropical marine estuary were investigated by measuring hydrocarbon concentrations in municipal wastewater treatment plants, urban stormwater drains, sediments, and benthic organisms in and around Tampa Bay, FL. The concentrations of petroleum hydrocarbons discharged from secondary and tertiary treatment plants in this area were lower than concentrations previously reported for other treatment plants in temperate regions. Samples collected from urban storm drains under base flow conditions were also low. The generally low levels of petroleum hydrocarbons in the sediments and organisms throughout Tampa Bay suggest that the bay is relatively pristine with respect to petroleum hydrocarbon contamination. Since it is unlikely that the anthropogenic input of hydrocarbons to this estuary is significantly lower than in other urbanized areas, we suggest that elevated annual temperatures in this subtropical system result in increased metabolic rates of microorganisms and more rapid degradation or metabolism of the petroleum hydrocarbons.     

Radon emanation from NORM-contaminated pipe scale and soil at petroleum industry sites

Radon-222 emanation fractions were determined for barite scale deposits associated with petroleum production tubing and soil contaminated with naturally occurring radioactive material (NORM). Samples were analyzed for 226Ra concentration, the results of which were used to calculate the 222Rn emanation fraction for the sample. An important parameter determining the overall Rn activity flux from a solid medium, 222Rn emanation fraction represents the fraction of 222Rn produced that enters the interconnected pore space within a medium contaminated with 226Ra before the 222Rn undergoes radioactive decay. The primary objective of the study was to determine whether 222Rn emanation fractions from pipe scale and soil from petroleum production sites are similar to those of uranium mill tailings. Pipe scale samples were collected at four sites representing a wide geographical area, and consisted primarily of barite scale where Ra atoms have replaced a fraction of the Ba within the crystal lattice of the scale. Soil samples were collected at five sites, from areas exhibiting elevated surface gamma exposure rates indicating the presence of NORM. For comparison, 226Ra concentrations and 222Rn emanation fraction were also determined for uranium mill tailings samples provided from a site in Utah. Although 2226Ra concentrations from pipe scale samples were similar to those found in uranium mill tailings, 222Rn emanation fractions from scale were generally lower. Emanation fractions from each data set were statistically different from those of mill tailings (p < or = 0.01). The differences are probably due to physical differences between the two media and to the method by which the Ra is deposited in the material. Radon emanation from soils was extremely variable owing not only to differences in physical and chemical soil properties, but also to the means by which NORM has entered the soil. Although additional emanation measurements from other sites are needed, the data collected at these sites indicate that regulations intended to protect human health from 222Rn inhalation should consider the type and properties of the medium in which the NORM is contained, rather than relying strictly on concentrations of the parent 226Ra.     

Screening plant species native to Taiwan for remediation of 137Cs-contaminated soil and the effects of K addition and soil amendment on the transfer of 137Cs from soil to plants

This study aims to screen plant species native to Taiwan that could be used to eliminate (137)Cs radionuclides from contaminated soil. Four kinds of vegetables and two kinds of plants known as green manures were used for the screening. The test plants were cultivated in (137)Cs-contaminated soil and amended soil which is a mixture of the contaminated one with a horticultural soil. The plant with the highest (137)Cs transfer factor was used for further examination on the effects of K addition on the transfer of (137)Cs from the soils to the plant. Experimental results revealed that plants cultivated in the amended soil produced more biomass than those in the contaminated soil. Rape exhibited the highest production of aboveground parts, and had the highest (137)Cs transfer factor among all the tested plants. The transfer of (137)Cs to the rape grown in the soil to which 100 ppm KCl commonly used in local fertilizers had been added, were restrained. Results of this study indicated that rape, a popular green manure in Taiwan, could remedy (137)Cs-contaminated soil.     

Bioremediation approaches for organic pollutants: A critical perspective

Due to human activities to a greater extent and natural processes to some extent, a large number of organic chemical substances such as petroleum hydrocarbons, halogenated and nitroaromatic compounds, phthalate esters, solvents and pesticides pollute the soil and aquatic environments. Remediation of these polluted sites following the conventional engineering approaches based on physicochemical methods is both technically and economically challenging. Bioremediation that involves the capabilities of microorganisms in the removal of pollutants is the most promising, relatively efficient and cost-effective technology. However, the current bioremediation approaches suffer from a number of limitations which include the poor capabilities of microbial communities in the field, lesser bioavailability of contaminants on spatial and temporal scales, and absence of bench-mark values for efficacy testing of bioremediation for their widespread application in the field. The restoration of all natural functions of some polluted soils remains impractical and, hence, the application of the principle of function-directed remediation may be sufficient to minimize the risks of persistence and spreading of pollutants. This review selectively examines and provides a critical view on the knowledge gaps and limitations in field application strategies, approaches such as composting, electrobioremediation and microbe-assisted phytoremediation, and the use of probes and assays for monitoring and testing the efficacy of bioremediation of polluted sites.     

Bioremediation approaches for organic pollutants: a critical perspective

Due to human activities to a greater extent and natural processes to some extent, a large number of organic chemical substances such as petroleum hydrocarbons, halogenated and nitroaromatic compounds, phthalate esters, solvents and pesticides pollute the soil and aquatic environments. Remediation of these polluted sites following the conventional engineering approaches based on physicochemical methods is both technically and economically challenging. Bioremediation that involves the capabilities of microorganisms in the removal of pollutants is the most promising, relatively efficient and cost-effective technology. However, the current bioremediation approaches suffer from a number of limitations which include the poor capabilities of microbial communities in the field, lesser bioavailability of contaminants on spatial and temporal scales, and absence of bench-mark values for efficacy testing of bioremediation for their widespread application in the field. The restoration of all natural functions of some polluted soils remains impractical and, hence, the application of the principle of function-directed remediation may be sufficient to minimize the risks of persistence and spreading of pollutants. This review selectively examines and provides a critical view on the knowledge gaps and limitations in field application strategies, approaches such as composting, electrobioremediation and microbe-assisted phytoremediation, and the use of probes and assays for monitoring and testing the efficacy of bioremediation of polluted sites.     

The Amoco Cadiz oil spill. Distribution and evolution of hydrocarbon concentrations in seawater and marine sediments

The shipwreck of the Amoco Cadiz supertanker on the rocks of the Brittany Coast of France (March, 1978) was one of the most disastrous oil spills ever recorded. The crude oils discharged in the marine environment were light petroleums. The distribution and the evolution of the oil pollution in the marine environment was examined. Chemical studies were limited to an overall estimate of the oil content to assess the importance and the extent of the pollution at the surface, in the water column, and in the sediment. UV fluorescence spectroscopy was used to detect oil in the seawater samples and IR spectrophotometry was used to analyze the sediment samples. Hydrocarbon concentrations in seawater ranged from 0.5 μ/1 to more than 100 μg/1. The oil spill has affected a very large section of the western English Channel. The diffusion of the hydrocarbons into the water column was observed. The evolution of the seawater pollution was followed, and the half-life of hydrocarbons in subsurface water was found to be between 11 and 28 days in different areas. One month after the disaster, the marine sediments were contaminated in the areas reached by the drifting slicks. The highest accumulation of petroleum in the sediments was located in the sheltered coastal environments. The natural decontamination process was found to be related to the nature of the sediment and the energy level of the geographic zone.     

Soil As contamination and its risk assessment in areas near the industrial districts of Chenzhou City, Southern China

In order to assess soil As contamination and potential risk for human, soil, paddy rice, vegetable and human hair samples from the areas near the industrial districts in Chenzhou, southern China were sampled and analyzed. The results showed that the anthropogenic industrial activities have caused in local agricultural soils to be contaminated with As in a range of 11.0-1217 mg/kg. The GIS-based map shows that soil contamination with As occurred on a large scale, which probably accounted for up to 30% of the total area investigated. Soil As concentration abruptly decreased with an increase in the distance from the polluting source. High As concentrations were found in the rice grain that ranged from 0.5 to 7.5 mg/kg, most of which exceed the maximal permissible limit of 1.0 mg/kg dry matter. Arsenic accumulated in significantly different levels between leafy vegetables and non-leafy vegetables. Non-leafy vegetables should be recommended in As-contaminated soils, as their edible parts were found in relatively low As level. Arsenic concentrations in 95% of the total human hair samples in the contaminated districts were above the critical value, 1.0 mg/kg, set by the World Health Organization. Arsenic could be enriched in human hair to very high levels without being affected by As containing water. The results revealed that the soils and plants grown on them are major contributors to elevate hair As in the industrial population. Therefore, the potential impact on human health of ingestion/inhalation of soil As around the industrial districts seems to be rather serious. Hence proper treatments for As contaminated soils are urgently needed to reduce the contamination.     

Photo-oxidation products of petroleum hydrocarbons in the Eastern Red Sea coastal waters

The level of dissolved oil residues as well as the oxygenated petroleum hydrocarbons in the seawater of the affected area of Jeddah coast, Red Sea was estimated. The dissolved/dispersed petroleum hydrocarbons concentration was found minimal. The minimum level may be attributed to the action of the weathering processes.Selected samples of the dichloromethane extracts of seawater were fractionated, using silica gel columns, into four fractions eluted with solvents of increasing polarity. The fluorescence intensity of these fractions was measured at three different pairs of excitation and emission wavelengths using ultraviolet fluorescence spectrofluorophotometry (UVF). The total fluorescence intensity of the fractions at 280 nm excitation, 327 nm emission wavelengths and 310 nm excitation, 360 nm emission wavelengths exceeds the fluorescence intensity of the whole extract by more than two orders of magnitude. The estimation of higher molecular mass oxygenated compounds in the fourth fractions, read at 380 nm excitation, 430 nm emission wavelengths, indicates rather low concentrations of <1 microg l(-1) hydroxypyrene equivalents. However, the polar fractions (eluted with acetone) account for more than 25% of the total fluorescence intensity of all fractions combined at each pair of wavelengths. The characterization of the products causing the fluorescence particularly the high molecular mass compounds still presents difficulties.Preliminary GC/MS results revealed some evidence for petroleum hydrocarbon oxidation products. Alkyl isobenzofuranones have been found in some seawater extracts. This is an ongoing project to characterize and identify additional compounds from these extracts.     

Distribution Of Cadmium And Nickel Among Various Forms In Natural And Contaminated Soils Amended With Edta

Because of its strong chelating capacity, application of ethylenediaminetetraacetic acid (EDTA) to soils may change the amount and distribution of heavy metals among their various chemical forms. Therefore, a greenhouse experiment was conducted using two cultivars of Brassica species (Brassica juncea and Brassica carinata) as hyper accumulator test crops on natural and artificially Cd and Ni contaminated soils. Both natural and metal amended soils were treated with disodium salt of EDTA at 0 and 1 g kg^–1 soil. After harvest of crops, soil samples were fractionated into water soluble plus exchangeable (WE), carbonate (CARB), organic matter (OM), Mn oxide (MnOX), amorphous Fe oxide (AFeOX), crystalline Fe oxide (CFeOX) and residual (RES) fractions. In metal amended soils, Cd and Ni were found predominantly in the AFeOX fraction in the absence of EDTA application and in the WE fraction in EDTA treated soil. Application of EDTA resulted in the redistribution of Cd among different forms and increased significantly Cd in the WE fraction with a concomitant significant decrease in the OM fraction. In natural soils, more than 40% of the total Cd was present in the RES fraction while in contaminated soil it was only 5%. Nickel in the WE fraction increased significantly while it considerably decreased in the CARB, OM, MnOX, AFeOX and CFeOX fractions with EDTA addition. This indicated that applied EDTA is capable to move Cd and Ni from the less soluble or more stable forms (CARB, OM, MnOX, AFeOX and CFeOX) to the most soluble form (WE). N natural soils, Ni in the RES fraction was found upto 49%, whereas only 10% of the total Ni was observed in contaminated soil, irrespective of EDTA treatment. In general, the amount of Cd recovered after harvest of both the Brassica cultivars did not differ significantly in any fraction except the WE fraction. The amount of Ni recovered in the AFeOX fraction was significantly higher after harvest of B. juncea as compared to B. carinata.Readers should send their comments on this paper to: BhaskarNath@aol.com within 3 months of publication of this issue.     

Natural and anthropogenic hydrocarbon inputs to sediments of Patos Lagoon Estuary, Brazil

The Patos Lagoon Estuary, southern Brazil, is an area of environmental interest not only because of tourism, but also because of the presence of the second major port of Brazil, with the related industrial and shipping activities. Thus, potential hydrocarbon pollution was examined in this study. Sediment samples were collected at 10 sites in the estuary, extracted, and analyzed by GC-FID and GC-MS for composition and concentration of the following organic geochemical markers: normal and isoprenoid alkanes, petroleum biomarkers, linear alkylbenzenes (LABs), and polycyclic aromatic hydrocarbons (PAHs). The total concentrations varied from 1.1 to 129.6 microg g(-1) for aliphatic hydrocarbons, from 17.8 to 4510.6 ng g(-1) for petroleum biomarkers, from 3.2 to 1601.9 ng g(-1) for LABs, and from 37.7 to 11,779.9 ng g(-1) for PAHs. Natural hydrocarbons were mainly derived from planktonic inputs due to a usual development of blooms in the estuary. Terrestrial plant wax compounds prevailed at sites located far from Rio Grande City and subject to stronger currents. Anthropogenic hydrocarbons are related to combustion/pyrolysis processes of fossil fuel, release of unburned oil products and domestic/industrial waste outfalls. Anthropogenic hydrocarbon inputs were more apparent at sites associated with industrial discharges (petroleum distributor and refinery), shipping activities (dry docking), and sewage outfalls (sewage). The overall concentrations of anthropogenic hydrocarbons revealed moderate to high hydrocarbon pollution in the study area.     

Which compounds contribute most to elevated airborne exposure and corresponding health risks in the Western Balkans?

A majority of ongoing monitoring of persistent organic pollutants (POPs) is currently focused on chemicals emphasized in the Stockholm Convention. Quantitative detection of other substances (especially those with numerous anthropogenic sources such as polyaromatic hydrocarbons (PAHs)) is, however, also needed since their concentrations are usually several orders of magnitude higher. A goal of this study was to determine how various groups of compounds contribute to total human health risks at the variety of sampling sites in the region of Western Balkan. Distribution of the risks between the gas and particulate phases was also addressed. Results showed that inhalation exposure to organochlorine pesticides (OCPs) does not represent a significant risk to humans, while polychlorinated biphenyls (PCBs) re-volatilized to the atmosphere from contaminated soils and buildings can pose a problem. PCB evaporation from primary sources (currently used PCB-filled transformers or non-adequate storage facilities) generally resulted in much higher atmospheric concentrations than evaporation from the secondary sources (soils at the sites of war destructions). A majority of the human health risks at the urban sites were associated with PAHs. Between 83 and 94% of the cumulative risk at such sites was assigned to chemicals sorbed to particles, and out of it, PAHs were responsible for 99%.     

New advances in plant growth-promoting rhizobacteria for bioremediation

Plant growth-promoting rhizobacteria (PGPR) are bacteria capable of promoting plant growth by colonizing the plant root. For a long period PGPR were mainly used for assisting plants to uptake nutrients from the environment or preventing plant diseases. Phytoremediation is a new and promising approach to remove contaminants in the environment. But using plants alone for remediation confronts many limitations. Recently, the application of PGPR has been extended to remediate contaminated soils in association with plants. Of all the present contaminants, the profound impacts of organic and heavy metal pollutants have attracted world wide attention. Here we review the progress of PGPR for remediation of soils contaminated with these two sources.     

Fate of oil from two major oil spills: Role of microbial degradation in removing oil from the Amoco Cadiz and IXTOC I spills

The fate of oil was examined in intertidal sediments impacted by the Amoco Cadiz spill in Brittany, France, and in surface waters contaminated by the IXTOC I well blowout in the Bay of Campeche, Mexico. The role of microbial degradation in removing the contaminating hydrocarbons was assessed by laboratory determinations of numbers of hydrocarbon utilizing microorganisms, measurement of microbial hydrocarbon biodegradation potentials, by chemical analyses of samples incubated under controlled conditions and by examination of the evolution of the hydrocarbon mixture in field samples collected after the spill. Analyses included the use of ¹⁴C radiolabelled hydrocarbon tracers, glass capillary-gas chromatography and mass spectrometry. Numbers of hydrocarbon utilizing microorganisms were found to be elevated by several orders of magnitude in oil contaminated samples. Numbers of hydrocarbon utilizing microorganisms appear to provide a useful index of environmental hydrocarbon contamination. However, environmental constraints on microbial processes appear to be most important in determining actual rates of biodegradation rather than numbers of available hydrocarbon utilizing microorganisms. Very high rates of degradation were found in intertidal sediments impacted by the Amoco Cadiz spill. In contrast, rates of degradation in the Gulf of Mexico were found to be much lower, partly due to nutrient limitations and partly due to the formation of large masses of oil-water emulsion or mousse.     

Effects of organic acids on copper and cadmium desorption from contaminated soils

A study was conducted to investigate the effect of organic acids on Cd and Cu desorption from natural contaminated soils (NCS) with permanent contamination by metal smelters and from artificial contaminated soils (ACS) derived from an artificial amendment of Cd to three representative zonal soils in Central China. Results showed that the desorption of Cd in either NCS or ACS, with the increment of tartrate or citrate concentration in desorption solution, can be characterized as a valley-like curve. The presence of tartrate or citrate at a low concentration (< or =0.5 mmol/l) inhibited Cd desorption from these two types of soils, whereas the presence of organic acids at high concentrations (> or =2 mmol/l for citrate and about > or =15 mmol/l for tartrate) apparently promoted Cd desorption. The desorption curve of Cu by tartrate solution with different tartrate concentrations can also be characterized as a valley-like curve, while the desorption of Cu in the presence of citrate was directly enhanced with the increment of citrate concentration. With the enhancement of initial pH value from 2 to 8 in the presence of citrate, Cu desorption ratio decreased at the first stage, then increased, and then decreased again. A valley and a peak sequentially appeared in the Cd or Cu desorption curve with initial pH value increment. Compared with citrate, the desorption ratio of Cd or Cu from NCS or ACS was directly decreased in the presence of tartrate, with the enhancement of the pH value from 2 to 8. Cd or Cu desorption was clearly enhanced when the electrolyte concentration of KNO3 or KCl increased in the presence of 2 mmol/l tartrate. Moreover, a higher desorption ratio of Cd or Cu was shown with KCl electrolyte than with KNO3 electrolyte with the same concentration. Based on these observations, we suggest that bioavailabilities of heavy metal can be promoted with selected suitable types and concentrations of organic acid amendment and reasonable field condition.     

Characteristics of microorganisms isolated from technogenic soils of the Kama region

Microorganisms capable of degrading monocyclic and polycyclic aromatic hydrocarbons and several chlorinated aromatic compounds were isolated from soils polluted with industrial waste from chemical plants. They were identified as representatives of the genera Pseudomonas, Flavobacterium, Alcaligenes, Rhodococcus, Microbacterium, Cellulomonas, Arthrobacter, and Brevibacterium. Among them, bacteria capable of utilizing xenobiotics in a wide range of ambient temperatures and pH and in the presence of high sodium chloride concentrations were revealed.