Phytoremediation of Soil and Water Contaminants - ACS Publications

Chapter 14

Field Study: Grass Remediation for Clay Soil Contaminated with Polycyclic Aromatic Hydrocarbons Downloaded by UNIV OF GUELPH LIBRARY on October 6, 2012 | http://pubs.acs.org Publication Date: April 8, 1997 | doi: 10.1021/bk-1997-0664.ch014

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Xiujin Qiu , Thomas W. Leland , Sunil I. Shah , Darwin L. Sorensen , and Ernest W. Kendall 3

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Central Research and Engineering Technology, Union Carbide Corporation, P.O. Box 8361, South Charleston, WV 25303 Utah Water Research Laboratory, Utah State University, Logan, UT 84322-8200 Union Carbide Remediation, Union Carbide Corporation, Houston, TX 77058 3

A three-year field-pilot study has demonstrated that Prairie Buffalograss (Buchloe dactyloides var. 'Prairie') has accelerated naphthalene concentration reduction in clay soil. Extensive soil sampling and analyses have been performed to evaluate statistically significant dif ferences between soil P A H concentrations with and without grasses. Comparative performance evaluation for other P A H compounds was restricted by analytical variability. A parallel experiment to assess the performances of twelve, warm season grass species from different ge netic origins has shown that Kleingrass (Panicum coloratum var. 'Verde') has a greater potential to remove PAHs from rhizosphere soil than other tested grasses at the site soil. Preliminary data indicated that Kleingrass root zone soil concentrations of both low and high molecu lar weight PAHs were approximately one order of magnitude lower than those with Prairie Buffalograss. Grass tissue analysis found no evidence of P A H bioconcentration. Food chain effects should not be a concern for phytoremediation of aged PAH-contaminated soils. Addi tional soil sampling is planned in the future to confirm the findings. PAH-contaminated clay soils are frequently observed at petrochemical manufacturing sites. Engineered remedial technologies based on excavation and subsequently ther mal or chemical treatment often entail high cost and a greater health risk by transfer ring contaminants to atmosphere. Applications of in-situ biotechnologies to date are mostly limited to the treatment of water-soluble contaminants associated with high permeability soils. Hydrophobic PAHs sorbed onto clay soils are difficult to treat, because of mass transfer restrictions. Union Carbide intends to develop a low cost and low risk technology using vegetation. Several laboratory studies have been con ducted since 1989 in collaboration with Utah State University. The results were promising (1,2,3,4). A grass remediation field-pilot study was started in 1992 to evaluate grass-rhizosphere effects on P A H degradation under field conditions and to identify competent grass species. A previous publication in 1993 presented field study methodology and preliminary results (5). This paper updates the results after three years of monitoring. 186

© 1997 American Chemical Society

In Phytoremediation of Soil and Water Contaminants; Kruger, E., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997.

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Downloaded by UNIV OF GUELPH LIBRARY on October 6, 2012 | http://pubs.acs.org Publication Date: April 8, 1997 | doi: 10.1021/bk-1997-0664.ch014

Background PAH degradation in soil and sediment is slow, although a wide variety of pure cul tures ofbacteria, fungi and algae and their purified enzymes have the ability to me tabolize PAHs (6,7,8). Microbial activity is constrained in the natural environment by the availability of nutrients and electron acceptors. (9). PAH degradation rates are further restricted by the desorption kinetics, die population of PAH-degrading micro organisms, and the competing reaction for electron acceptor utilization (10,11,12). Microorganisms typically degrade PAHs aerobically by incorporating oxygen atoms into the ring structure generating dihydrodiols via oxygenases. The derivative is further mineralized through aromatic ring cleavage and subsequent oxidation (6). The biodégradation rates of PAHs are significantly higher under oxic conditions than those under anoxic ones. Low-molecular-weight PAHs (with two or three condensed benzene rings) are amenable to microbial degradation under aerobic and denitrifying environment. However, negligible biodégradation occurs under the sulfate-reducing or methanogenic environments (13,14,15). According to thermodynamic calculations high-molecular-weight PAHs (with four or more condensed benzenerings)are re ported theoretically nondegradable at low redox potentials (16). Moreover, highmolecular-weight PAHs do not serve as substrates for microbial growth, though they may be subject to cometabolic transformation (7 7,18,19). Heterotrophic microorganisms are responsible for the catabolic degradation of organic chemicals in nature, however, many are unable to degrade PAHs. Total het erotrophic population does not indicate the potential for PAH degradation by micro organisms. Prolonged exposure to chemical toxicants can cause adaptations in mi crobial populations that result in greater resistance to toxicity or enhanced ability to utilize toxicants as substrates for metabolism or co-metabolism. Studies have shown microbial adaptations and increased PAH degradation in response to chronic PAH exposure, but the actual mechanisms of these adaptations are not known (19,20). In situ bioremediation of PAH-contaminated clay soil is a challenge. The high adsorption capacity of clay soils may limit the amount of PAHs available to microor ganisms. The low flux of nutrients and electron acceptors through low permeability clay soil may also restrict microbial activities. An engineered process may accelerate biodégradation, however a system of delivering electron acceptors, substrates, nutri ents, and enzymes to numerous microsites would be technically and economically un feasible. Nevertheless, plant roots are known to perform suchlike functions. The rhizosphere provides a complex and dynamic microenvironment, where microbial communities associated with plant roots, have great potential for detoxifi cation of organic contaminants. Deep fibrous root system of certain grasses may im prove aeration in soil by removing water through transpiration and by altering clay soil structure through agglomeration. Plant release photosynthate to soil through ex udation and sloughing of dead root cells increases soil organic matter. Root exudates (carbohydrates, amino acids, etc.) sustain a dense microbial community in the rhi zosphere, which may enhance degradation, mineralization, and/or polymerization of organic toxicants (21). The consortium ofbacteria and fungi associated with the rhi zosphere may possess highly versatile metabolic capabilities (21). Certain root exu dates may support microbial cometabolism of high molecular weight PAHs, which bacteria and fungi cannot use as a sole carbon source (7). In addition, the greater soil organic content in rhizosphere soil may alter toxicant sorption, bioavailability, and leachability (22). Plants use a variety of reactions to degrade complex aromatic structures to more simple derivatives. Aromaticring-cleavagereactions in plant tissues, which lead to complete catabolism of the aromatic nuclei to carbon dioxide, have been re ported (23). Benzo[a]pyrene, a five-ring PAH, can be metabolized to oxygenated de rivatives in plant tissues (24). Although some of these derivatives are known to be



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more toxic than the original compounds, they appear to be polymerized into the in soluble plant lignin fraction, which may be an important mechanism for their detoxi fication. With plant seedlings, Benzo[a]pyrene was assimilated into organic acids in cluding amino acids (25). Complete degradation of Benzo[a]pyrene to carbon dioxide was also observed with a wide range of plants (25). A well-established grass cover conserves soil and substantially reduces the risk of exposure to soil contaminants. PAHs associated with soil generally do not pose arisk,unless soil particles are transported to a receptor via direct ingestion, in halation, or dermal contact. Owing to their hydrophobic nature, PAHs have poor mo bility. High-molecular-weight PAHs are virtually immobile with water flux. Al though PAH degradation, mineralization, and polymerization in soil may take consid erable time, grasses reduce theriskto human health and the environment immediately after a dense grass ground cover is developed. Grasses also significantly reduce po tential contaminant migration via surface runoff and any infiltration to groundwater. Risk may arisefromplant bioconcentration of carcenogenic PAHs via food chains due to animals grazing grasses. Many plant roots and shoots are capable of bioconcentrating soil-borne chemicals such as pesticides and petroleum compounds. Plant concentration of PAHs has been reported (25,26,27,28,29). However, PAHs are mostly accumulated in the roots and not translocated to plant shoots because of their hydrophobic nature (26,29). In summary, PAH degradation in clay soil may be limited by low redox po tential, desorption kinetics, lack of responsible microbial population, and lack of nu trients. A plant root zone system may facilitate PAH biodégradation. Planting grasses substantially reduces theriskof exposure to contaminated soils and may ulti mately transform PAHs to innocuous products (C0 and H 0). PAHs may be bioconcentrated to plant roots, however, are not translocated to plant shoots. Therefore, animal grazing grasses should not cause subsequentriskthrough food webs. 2

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Methods Several laboratory studies had been conducted prior to thisfield-pilotstudy. PAH disappearance was enhanced in the presence of prairie grasses and cow manure in a screening study(7). Subsequent soil microcosm studies using radiolabeled PAH com pounds showed that a variety of native grasses enhanced PAH mineralization and in corporation into soil organicfraction(2,3,4). To evaluate the grass effects under field conditions we initiated a field study at Union Carbide Seadrift Plant in Texas. Three plots were constructed at the olefins' production area between the old foundations of a demolished natural gas compressor building. Plot 1 (10 ft χ 20ft)was an unvegetated control. Plot 2 (10 ft χ 20ft)was sodded with Prairie Buffalograss. These two main plots were designed to evaluate the grass rhizosphere effects on PAH degradation in clay soil by periodic sampling and analysis. Plot 3 (10 ft χ 90ft)was designed to screen the performance of a variety of grassesfromdifferent genetic origin mainly by visual observation. Unlike the laboratory studies, PAH concentrations in field were highly vari able. Sufficient number of samples must be taken to accurately estimate the statistical significance of vegetation effects. A systematic randomized sampling strategy was used to reduce sample variance (5). Field PAH concentrations displayed a lognormal distribution. Geometric mean with its corresponding confidence limit is the appropri ate estimate of central tendency. Log concentration data were used throughout the statistical analysis using JMP® computer software (SAS Institute, Inc,). Detailed field-study methodology can be found in Qiu, 1994 (5).



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Experimental design. A three-way factorial design model had been proposed in our earlier publication to test the statistically significant differences in soil PAH concen trations for the effects of vegetation treatment, soil depth, and treatment time. This test model was rather inappropriate, because of serious systematic variability in the field experiments. The experiments were not exclusively comparative with regard to sampling depths, plots, and sampling times. First, PAH concentrations were corre lated with soil depths before treatment. Concentrations in surface soil (0 -1ft)were significantly higher than those in subsurface soil (>1ft)(31). Because of the nonrandom vertical concentration distribution, the surface and subsurface soil should be con sidered as subgroups in a stratified population. In addition, the vegetation treatment effects on surface soil were essentially differentfromthose on the subsurface soil. During the three years of treatment, the grass roots penetrated less than one foot deep. No rhizosphere had developed in the subsurface soil, but the grass root exudates leaching down to the subsurface soil may have altered PAH sorption, bioavailability, and leachability. Secondly, systematic variation among the six sampling and analysis events was possible due to differences in analytical procedures, sampling tempera tures, and sample holding time. To eliminate the known sources of discrepancies, a nested design model was used to separate the total variation into parts assignable to various sources, i. e., vegetated versus control plots, soil depths, and treatment times. Table I shows a 2 χ 7 χ 2 nested design with the three sources of variation and ten replicates. The test soil was divided into two depths, surface (0 -1ft)and subsurface (1-4 ft). Each depth is to be independently sampled seven times (six rounds completed so far). For each sampling time, ten replicate samples have been taken from each of the two plots, vegetated and unvegetated control at each depth, yielding a total of 40 samples per event. Analysis of variance (ANOVA) estimated three separate component variances: the variance from surface to subsurface soils, the variancefrombetween treatment pe riods, and the variancefromvegetated to unvegetated control plots. Statistical sig nificance was tested for the effects of vegetation treatment, treatment time, and soil depth. Table I. A 2 χ 7 χ 2 Nested Experimental Design with Ten Replicates Source of Variation SubsurjaceSol(l-4jt) Depth Surface Soil (0-1 β) Treatment 162 301 462 757 1045 0 162 301 462 757 1045 Time (days) 0 Plot C V C V C V C V C V C V c V C V C V C V C V C V C V C ν Number of 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Replicate

(where, C = unvegetated control plot and V = JBu Halograss-vegetated plot) Sample Analysis. Thefieldsoil samples were extracted by Soxhlet extraction and the extracts were analyzed for PAHs by GC/MS (gas chromatography/mass spectro photometer) for the four earlier sample sets. We were unable to detect high molecular weight PAHs (HMW PAHs) and several low molecular weight PAHs (LMW PAHs) by GC/MS. The machine used had relatively high quantitation limits (QL), ranging from 5 to 7 mg/kg-soil. The HMW PAH and several LMW PAH concentrations in the site soils rangedfromapproximately 0.1 to 5 mg/kg-soil. To obtain data neces sary we implemented an analytical method to lower QL for PAHs to below the PAH cleanup standards. The method uses HPLC with UV and fluorescence detector in se ries (a modification of EPA SW846 method 8310) achieving a QL of 100 mg/kg) was significantly higher than those of other PAHs (95% confidence level, while they were insignificant on Days 162 and 462 (31). For subsurface soil, there were no significant differences in the naphthalene concentrations at 95% confidence level between vegetated and control plots during the course of treatment.

Vegetated w/ Buffalograss (subsurface soil)

Unvegetated Control (surface soil)

Unvegetated control (subsurface soil) Vegetated w/ Buffalograss (surface soil) 200

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Figure 1. Naphthalene concentrations in surface soil over time

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Figure 2. Naphthalene concentrations in subsurface soil over time


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The statistical analysis excludes time zero concentration data, because we did not have good quality control in chemical analysis at time zero. Statistical analysis indi cated an enhanced naphthalene concentration reduction in rhizosphere soil. However, overlying vegetation had no significant effects on the subsurface soil where grass roots had not yet developed, perhaps due to extremely wet condition. The field naphthalene concentration data did not fit a typical first order degra dation rate model, therefore the correspondent degradation rate can not be derived. However, ANOVA showed that naphthalene concentration in surface soil signifi cantly decreased over time for both vegetated and unvegetated control plots (57). A slow dissipation of naphthalene in the control soil indicated a potential intrinsic deg radation of naphthalene in the site soil. Rhizosphere Effects on Other PAH Compounds. Comparative performance evaluation for other PAH compounds was restricted by analytical variability. Soil PAH data (last two sets analyzed by HPLC) show no significant changes in PAH concentrations between Days 757 (Sept. 1994) and 1045 (Jun. 1995). Unfortunately, the GC/MS used in analyzing the earlier four sets of samples failed to accurately quantify PAHs other than naphthalene, because the concentration levels were either below or marginally higher than the quantitation limit. Figures 3 and 4 show LMW and HMW PAH concentrations in soil for the Buffalograss plot and the control plot, respectively. Table II presents whether the dif ferences in PAH concentrations between Buffalograss and control plots were statisti cally significant or not. Interestingly, all PAHs concentrations in subsurface soil were higher in vegetated plot than those in the control plot. So were most PAHs in surface soil, except for four LMW PAHs, despite that the differences were mostly insignifi cant at 95% confidence level in the surface soil, except for the seven heavier HMW PAHs in 1994. Conversely, the differences were mostly significant in the subsurface soil, except for the five LMW PAHs in year 1995. Most LMW PAH (except fluoranthene) concentrations in vegetated surface soil were lower than those in control surface soil, although this difference was only significant for naphthalene. We do not know whether these results were simply due to sampling and analysis variability or caused by complex physicochemical and biological processes in the test plots. How ever, similar pattern was also observed in the surface soil for several other grasses as discussed later.

Figure 3. Comparison of low-molecular-weight PAH concentrations in soil (94 = samples taken on day 757 in 1994; 95 = samples taken on day 1045 in 1995; cont = unvegetated control plot; and vege = Buffalograss-vegetated plot)



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Figure 4. Comparison of high-molecular-weight PAH concentrations in soil (94 = samples taken on day 757 in 1994; 95 = samples taken on day 1045 in 1995; cont = unvegetated control plot; and vege = Buffalograss-vegetated plot.) TABLE II. Statistical Significant Differences in Soil PAH Concentrations Sample Depth Sample Time Compound

Surface (0 -1ft) 1994

1995

Subsurface (I-2 ft) 1994 1995

Soil concentrations significantly diflferent between BufTalograssvegetated and unvegetated control filots? Control

Vege

Control

Vege

Control

Vege

Control

Vege

Naphthalene High Low High Low No No No No Acenaphthene No No No No Low High No No Fluorene No No No No Low High No No Phenanthrene No No No No Low High No No Anthracene No No No No Low High No No Fluoranthene No No No No Low High No No Pyrene No No No No Low High Low High Benzo[a]anthracene No No No No Low High Low High Chrysene Low High No No Low High Low High Benzo[b]fluoranthene Low High No No Low High Low High Benzo[k]fluoranthene Low High No No Low High Low High Benzo[a]pyrene Low High No No Low High Low High Low High Dibenz[a,h]anthracene Low High No No Low High Benzo[g,h,i]perylene Low High No No Low High Low High Indeno[ 1,2,3,cd]pyrene Low High No No Low High Low High Where, control = unvegeltated control plot; vege = Bullalograss-vegetatecIplot; No = statistically insignificant between unvegetated-control and Buffalograss-vegetated plots; Low = significantly low; and High = significantly high.

If the results were not simply owing to the sampling and analysis variability, then why were soil PAH concentrations in the vegetated plot in most cases higher than those in unvegetated control plot? Could it be caused by the differences in sol vent extractability of PAHs incorporated in soil matrix? The presence of organic ac ids and phenols released from grass roots may increase the apparent solubility of hy drophobic compounds. Over time hydrophobic PAHs may be more extractable and bioavailable. While the LMW PAHs could have been degraded, HMW PAH degra dation could be more slowly or could have been recalcitrant under the likely anoxic conditions.



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Mihelcic et al. reported that acenaphthene and naphthalene in soil slurry biodegraded under denitrifying conditions (10). Leduc et al. reported that biodégradation of acenaphthene, acenaphthylene, fluorene, and anthracene occurred under aerobic and denitrifying environment, however, it was insignificant under the sulfate-reducing or methanogenic environments. Degradation of HMW PAHs under anoxic conditions has not been reported. Soil redox potentials were not measured during the study, however, near saturated conditions were known to exist very often as a result of poor site drainage and intermittent flooding. While the surface soil may be aerated occa sionally, the subsurface soil may have been constantly under anaerobic conditions. The latter was exasperated by arising capillaryfringeof the shallow ground water ta ble. Even LMW PAHs would be recalcitrant under sulfate reducing or methanogenic environment. Annual fertilization has supplied a large amount of nitrate, which can be used as electron acceptor under denitrifying conditions. Fertilization could have stimulated LMW PAH degradation in the test plot. Mihelcic et al. reported that the significance of PAH degradation under denitrifying condition in the field depends on the avail ability of nitrate, as well as on the ratio of PAH compound to the mineralizable or ganic carbon content, typically less than 1.4% of the total natural soil organic carbon (32). The latter competes for nitrate utilization. Therefore, the effects of root exuda tion may be complicated. Furthermore, the increases of soil organic content in vegetated plot may cause more PAHs partitioning onto soil organic matter and reduce their water solubility. Manilal and Alexander found that the rate of phenanthrene mineralization was slower in an organic soil than that in a mineral soils with lower organic content (9). Mihelcic et al. and Al-Bashir et al. reported that the sorption-desorption interactions with soil may limit the amount of total PAH compound available to the microorganisms and control the rate of mineralization (10,12,13). Further study is necessary to determine the vegetation effects on PAHcontaminated soils, especially for carcinogenic HMW PAHs. The rhizosphere effects on PAH removal, including complex interactions among sorption, degradation, hy drolysis, mineralization, and humification, are not well understood. Other research needed includes establishing environmentally acceptable cleanup standards for phytoremediation, based on potentialrisksto human health and the environment. This study suggested that PAHs incorporated in aged contaminated soil may not be completely extractable by organic solvents, meanwhile only afractionof the organic solvent extractable PAHs is water soluble, presumably bioavailable. The fraction may be a function of soil physicochemical and biological characteristics. The organic solvent-extractable PAH concentrations in aged contaminated soil do not measure a realrisklevel to human health and the environment. Analyzing site-specific soil characteristics is particularly important, when conducting phytoremediation,riskas sessment, and determining cleanup goals. Buffalograss Root Development. High soil moisture content suppressed Buffalograss root development. Buffalograss is drought tolerant, but suffers in wet soil. Fig ure 5 shows the Buffalograss root zone depth over time. Grass roots developed mostly during the second year, when the weather was unusually dry. During the first and the third years, repeated abnormal heavy precipitation and the poor drainage con dition caused intermittent water logging in die test plot, which severely inhibited grass root development. The site is suiTounded by above ground cooling water ba sins, resulting in high groundwater table. The local Lake Charles clay soil has very low permeability. Soil moisture content analysis indicated that the test plot soil may have been seasonally or permanently saturated, excluding airfromthe soil pores and resulting in anaerobic conditions. Grass roots were reluctant to extend downward into anaerobic soil environment. A parallel green house study demonstrated that PAH re-


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moval was enhance due to small decreases in moisture content (small increase in airfilled porosity) in soil near saturation (33). Managing soil moisture content at optimal levels is important for biodégrada tion and plant growth. A drainage system controlling soil saturation level would be desirable where economically feasible. Selectively growing water-tolerant plants, ca pable of removing excessive soil moisture and maintaining appropriate soil redox potential may be a low-cost alternative.

Figure 5. Prairie Buffalograss root depths over time Identifying Competent Grass Species. Twelve warm season plant species, naturally adapted to the coastal areas of Texas, from different genetic origins are being tested at Plot 3. A competent grass species must possess anatomical, biochemical, and physiological adaptations to the sitespecific environmental condition. The important characteristic is a deep, dense root zone system to improve soil aeration condition and selectively foster PAH-degrading bacteria growth. Table III lists their names and application forms. Most of the spe cies selected are short grasses along with three tall grasses. Also we included two herbaceous plants, natural flowers, to examine the potential of plants other than grasses. Switchgrass was planted in the second study year replacing Bluegramagrass. The latter did not grow. The two natural flowers had germinated, but died soon after, perhaps the soil was too wet. Experimental Design and Methods. A randomized complete block experiment was designed to assess the performance of the twelve grass species. Plot 3 is divided into three blocks. Each block contains twelve experimental units. Each unit has a size of 5 ft χ 5 ft. The twelve species were randomly located on the twelve units within a block. Each grass has triplicate experimental units located in the three blocks, re spectively. Periodic visual observations have been conducted unit by unit to evaluate: 1) rate of seed germination; 2) percentage survival of seedlings or solid sodding; 3) grass density and height; and 4) extent of root zone establishment. Appraisal is based on a nine-grade grading criteria. Root zone soils were sampled and analyzed for PAHs after three years.


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TABLE III. Twelve Plant Species Tested on Plot 3


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Name

Type

Application Form

Short grass Seashore Paspalum Paspalum vaginatum var. 'Adalayd' Short grass Buffalograss Buchloe dactyloides var. 'Prairie' Short grass Bermudagrass Cynodon dactylon var.'Texturf 10' Short grass Zoysiagrass Zoysiajaponica var. 'Meyer' St. Augustinegrass Stenotaphrum secundatum var. 'Raleigh'Short grass Short grass K.R. (King Ranch) Bluestem Bothriochioa ischaemum Short grass Common Buffalograss Buchloe dactyloides Tall grass Weeping Lovegrass Eragrostis curvula Tall grass Kleingrass Panicum coloratum var. 'Verde' Tall grass Switchgrass Panicum virgatum var. 'Alamo' Herbaceous Texas Bluebonnet Lupinus texensis Winecup Callirhoe involucrata Herbaceous

Sod Sod Sod Sod Sod Seed Seed Seed Seed Seed Seed Seed

Performance Evaluation. Performances of the twelve grasses were evaluated based on visual appearance, root zone development, and root zone soil PAH concentration level. Visual Appearance. Statistical analysis of the visual appearance grading data showed that the top five grasses above average are (1) Verde Klein, (2) Zoysia (3) Bermuda, (4) Prairie Buffalo, and (5) Common Buffalo. Verde Kleingrass was sig nificantly better than all but Zoyzia and Bermuda, while the latter two were not sig nificantly better than Praire Buffalo or Common Buffalo. There were no significant differences in visual appearances between tall and short grasses, between seed and sod forming grasses, and among the three blocks. Verde Kleingrass appears the most healthy, dense, and the best ground coverage. Root zone development. After 3-year growth the Verde Kleingrass and the Common Buffalograss developed deeper roots than the others (Figure 6). Zoysiagrass and Bermudagrass displayed relatively dense but short roots. The vertical error bars are standard deviations among the triplicate experimental units. The root zones of other grasses were either poorly developed or never developed at all.

Figure 6. Comparison of root depths among different grass species



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Soil PAH Concentrations Associated with Different Grass Species Two of the top five grasses, Common Buffalo and Zoysia had similar PAH concentration lev els in root zone soil to Prairie Buffalograss, but Verde Kleingrass. Root zone soils were collected from each of the triplicate experimental units of three top-grading grasses, Verde Kleingrass, Meyer Zoysiagrass, and Common Buffalograss, after three years of growth. Bermudagrass plots were not sampled. For each grass two compos ite soil samples were analyzed for PAHs. Figure 7 shows that the mean soil concen trations of LMW PAHs, associated with the four grasses, including Prairie Buffalograss (plot 2) were generally lower than those with the control (plot 1). The concen trations associated with Verde Kleingrasses were either nondetectable or approxi mately one to two orders of magnitude lower than those with the other grasses and the control. The mean soil concentrations of HMW PAHs, associated with three grasses, except Kleingrass, were close to or higher than those with the control (Figure 8). Still, the soil HMW PAH concentrations in Verde Kleingrasses root zone soil were much lower than those in the control soil. To verify the differences between grass species, more soil samples were collected from each of the triplicate experimental units of six grasses, including Klein, Bermuda, Switch, Common Bufflo, Zoysia, and St. Augustine, in May 1996. Analytical results indicated that root zone soil PAH concentrations of Kleingrass and Bermudagrass were significantly lower than those of the other four grasses. Additional soil sampling and analysis are planned in 1997 or later to obtain sufficient data for statistical analysis.

Figure 7. Comparison of LMW PAH concentrations in root zone soils of the four top-grading grasses against unvege tated control

Figure 8. Comparison of HMW PAH concentrations in root zone soils of the four top-grading grasses against unvege tated control

Kleingrass appeared to have a greater potential to remove PAH compounds from rhizosphere soil than other tested grasses. It withstood sustained water-logging and exceptional seasonal drought and developed healthier, deeper, and dense roots in the clay soil. This bunch-type tall grass with deepfibrousroots may be naturally fit for the field soil. According to USDA's soil survey, the local Lake Charles clay soil formed under a dense stand of tall grasses. We do not know whether the possible en-


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hanced removal of PAHs was simply due to the improved soil aeration condition or a series of complex chemical and/or enzymatic reactions in the presence of a unique substrate secretedfromKleingrass roots. Researchers reported that many het erotrophic bacteria in natural soil are unable to degrade PAHs. Only a small adapted population respond to PAH degradation (1 7,18). Despite the many uncertainties, we believe that certain plants have the potential of remediating PAH-contaminated soils by influencing soil chemistry and biochemistry, improving oxygen transport for mi crobial activities, and perhaps selectively fostering PAH-degrading bacteria growth.


Bioconcentration Risk arisingfromplant bioconcentration of PAHs has been studied, because most HMW PAHs are known to be carcinogenic (55). Animals feeding on the plant might receive high doses of the PAHs and cause subsequentrisksvia food chain. We ex amined potential bioconcentration of PAHs to grass tissues at our test plots. Grass shoot and root tissues were collected from all the experimental units of Verde Kleingrass, Meyer Zoysiagrass, Prairie Buffalograss, and Common Buffalograss. Soil particles clinging on the roots were removed by ultrasonic water bath. Duplicate composite tissue samples were soxhlet extracted and analyzed for PAH concentrations. No PAHs were detected from either shoots or roots. Figures 9 and 10 shows the detection limits of the LMW and HMW PAHs in grass tissue versus the as sociated soil concentrations, respectively. Contrary to several published reports (26,27,28,29), our study showed no PAH bioconcentration in the plant shoots or roots. Previously published data are ei therfrommunicipal wastewater sludge tests orfromlaboratory experiments, in which PAH compounds were freshly spiked onto the soil. Those experiments may not re flectfieldapplication of phytoremediation, where plants grow on aged-contaminated soils. Freshly supplied chemicals in laboratory soils or municipal sludges remaining on the exterior surface of soil/sludge particles could have a chance to partition onto plant root surfaces. However, as a contaminated site aged, the PAHs at the exterior soil aggregate surfaced would have already degraded or been transported away. The remaining portion, mainly trapped in or adsorbed to the interior surfaces of soil

Figure 9. Comparing the detection limits of LMW PAHs in grass tissue to the associated soil concentrations

Figure 10. Comparing the detection limits of HMW PAHs in grass tissue to the associated soil concentrations


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micropores, would have little chance to redistribute to plant roots. According to the theoretical calculation of bioconcentration factors, P A H concentrations in the grass shoots and roots would be less than the detection limits of this study (33). Neither food chain effects nor volatilization through leaves should be a concern for phytore mediation of aged PAH-contaminated soils.


Conclusions Prairie Buffalograss accelerated naphthalene concentration reduction in soil, despite the fact that high soil moisture content has suppressed grass root development. The field soil P A H concentration reduction did not fit the first order reaction kinetics and the corresponding rate can not be derived. Comparative performance evaluation for other P A H compounds was restricted by analytical variability. P A H degradation in soil could have been limited by low redox potential and desorption kinetics. A drainage system controlling soil saturation level would be desirable where economically feasible. Selectively growing water-tolerant plants, capable of remov ing excessive soil moisture and maintaining appropriate soil aeration condition may be a low-cost alternative. Verde Kleingrass demonstrated a greater potential to remove PAHs from wet clay soil than the other tested grasses. The Kleingrass roots were well established in the wet clay soil. After three years of growth, it's root zone soil concentrations for both low and high molecular weight PAHs were approximately one order of magni tude lower than those associated with Buffalograss. Contrary to several published reports, no bioconcentration of PAHs in the grass shoots or roots was observed. Previously published data from experiments with freshly supplied chemicals may not reflect actual field conditions, where plants grow on aged-contaminated soils. Neither food chain effects nor volatilization through leaves should be a concern for phytoremediation of aged PAH-contaminated soils. Acknowledgments Union Carbide Seadrift Plant EP Department performed the pilot study. Field per sonnel included Mr. Joe Padilla, Mr. Trinidad Gomez, Mr. Marcus May, and Mr. Joe Stubbs. The authors thank Mr. Steve Galemore, Mr. Craig Falcon, Mr. David McMahon, Mr. Jack Batterola, and Mr. Ron Pace for their administrative support. At Utah State University, Dr. Ronald C. Sims is the principal investigator of the program. Mr. Venubabu Epuri, Mr. Jeff Watkins, Dr. Ari Ferro, Mr. Wyne April, and Mr. James Herrick contributed to laboratory studies and/or field sample analysis. Special thanks go to Dr. Milton C. Engelke, Texas A & M University, for his valuable input to this study. Thanks are due to Mr. John Matthews and Mr. Scott G. Huling, USEPA Kerr Laboratory, and Dr. Daniel F. Pope, Dynamac Corporation, for partially funding the studies at Utah State University. The author sincerely thanks Mr. Richard A . Conway and Dr. James L. Hansen for their helpful discussion. Literature Cited 1. April, W; Sims, R.C. Chemosphere. 1990, 20(1-2):253-265. 2. Ferro, A.M.; Sims, R.C; Bugbee, B.G. J. Envir. Quality. 1994, 23(2):272-279. 3. Watkins, J.W.; Sorensen, D.L.; Sims, R.C. In Bioremediation through Rhi zosphere Technology; Anderson Τ. Α.; Coats, J.R. Eds.; A C S Symposium Series 563; American Chemical Society: Washington, DC, 1994, pp 123-131. 4. Epuri, V.; and Sorensen, D.L. In Phytoremediation of Soil and Water Contami nants; Kruger, E.L., Anderson T.A. and Coats, J.R., Eds.; A C S Symposium Se ries; (American Chemical Society: Washington, DC. in press).



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5. Qiu, X . ; Shah, S.I.; Kendall, E.W.; Sorensen, D.L.; Sims, R.C.; Engelke, M . C . In Bioremediation through Rhizosphere Technology; Anderson T.A.; Coats, J.R. Eds.; ACS Symposium Series 563; American Chemical Society: Washington, DC, 1994, pp 142-159. 6. Cerniglia, C.E. Adv. Appl. Microbiol. 1984, 30:31-71. 7. Kihohar, H.; Nagao, K. J. Gen. Microbiol. 1978, 105:69-75. 8. Schocken, M.J.; Gibson, D.T. Appl. Environ. Microbiol. 1984, 48:10-16. 9. Manual, V . B . ; Alexander, M. Appl. Microbial. Biotechnol. 1991, 35:401-405. 10. Mihelcic, J.R.; Luthy, R.G. Appl. Envir. Microbiol., 1988, 54(5):1188-1198. 11. Raddy, K.R.; Rao, P.S.C.; Jessup, R.E. Soil Sci. Soc. Am. J. 1982, 46:62-68. 12. Al-Bashir, B.; Cseh, T.; Lecuc, R.; Samson, R. Appl. Miocrobiol. Biotechnol. 1990, 34:414-419. 13. Mihelcic, J.R.; Luthy, R.G. Appl. Envir. Microbiol., 1988, 54(5):1182-1187. 14. Leduc,R.; Samson,R.; Al-Bashir,B.; Al-Hawari, J.; Cseh, T. Wat. Sci. Tech. 1992, 26(1-2):51-60. 15. Bauer, J.E.; Capoint, D.G. Appl. Envir. Microbiol., 1985, 50:81-90. 16. McFarland, M.J.; Sims, R.C. Journal of Groundwater, 1991, 29(6):885-698. 17. Keck, J.; Sims, R.C.; Coover, M.; Park, K.; Symons, B . Water Res., 1989, 25(12):1467-1476. 18. Bulman, T.; Lesage, S.; Fowlie P.J.A.; Weber, M.D. PACE Report; Petroleum Association for Conservation of the Canadian Environment, Ottawa, Canada, 1985, 85-2. 19. Cernignia, C.E.; Heitkamp, M . A . In Metabolism of Polycyclic Aromatic HydroCarbons in the Aquatic Environment. Varanasi, U. Ed.; CRC Press, Inc.: Boca Raton, FL, 1989, pp 41-68. 20. Grosser, R.J.; Warshawsky, D.; Vestal, J.R. Envir. Toxicol. Chem. 1995, 14(3):375-382. 21. Fitter, A . H . ; Hay, R . K . M . Envir. Physiology, 2nd Ed. Academic Press, London, U K , 1987, pp 423. 22. Walton, B.T.; Guthrie, E.A.; Hoylman, A . M . In Bioremediation through Rhi zosphere Technology; Anderson Τ. Α.; Coats, J.R. Eds.; ACS Symposium Series 563; American Chemical Society: Washington, DC, 1994, pp 11-27. 23. Ellis, B.E. Lloydia. 1974, 37(2):168-184. 24. Harms, H.; Dehren, W.; Monch, W. Ζ. Naturforsch. 1977, 32:321-326. 25. Sims, R.C.; Overcash, M.R. Residue Revs. 1983, 88:2-68. 26. Ellwardt, P. Proc. Series - Soil Organic Matter Studies. 1977, 2:291-298. 27. Muller, V . H . Ζ Pflanzenernaehr. Bodenkd. 1976, 6:685-695. 28. Topp, E.; Scheunert, I.; Attar,A.; Korte, F. Ecotoxicol. Environ. Safety. 1986, 11:219-228. 29. Harms, H.; Sauerbeck, D. Angew. Botanik. 1984, 58:97-108. 30. Qiu, X . Field Scale Pilot Study: Vegetation Enhanced Soil Bioremediation, 1993-1994 Annual Progress Report; Union Carbide Corporation: Tech. Center, South Charleston, WV, 1995. 31. Qiu, X . Field Scale Pilot Study: Vegetation Enhanced Soil Bioremediation, 1994-1995 Annual Progress Report; Union Carbide Corporation: Tech Center, South Charleston, WV, 1996. 32. Raddy, K.R.; Rao, P.S,C.; Jessup, R.E. Soil Sci. Soc. Am. J. 1982, 46:62-68. 33. Leland, T.W. Matric Potential, Vegetation, and Mycorrizae Effects on PAH Deg radation in Clay Soil. M S Thesis. Dept. of CEE, Utah State University: Logan, UT, 1996. 34. Warshawsky, G.D.; Vestal, J.R. Envir. Toxicol. Chem. 1995, 14:3:375-382. 35. Bell, R . M . Higher Plant Accumulation of Organic Pollutants from Soils; EPA/600/R-92/138; PB92-209378; NTIS: Springfield; V A , 1992, pp 127.


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