Effects of pig manure compost and nonionic-surfactant Tween 80 on phenanthrene and pyrene removal from soil vegetated with Agropyron elongatum

This paper evaluates the effects of pig manure compost (PMC) and Tween 80 on the removal of phenanthrene (PHE) and pyrene (PYR) from soil cultivated with Agropyron elongatum. Soils spiked with about 300mgkg(-1) of PHE and PYR were individually amended with 0%, 2.5%, 5% and 7.5% (dry wt) of PMC or 0, 20 and 100mgkg(-1) of Tween 80. Unplanted and sterile microcosms were prepared as the controls. PAH concentration, total organic matter (TOM), dissolved organic carbon (DOC), total heterotrophic and PAH degrading microbial populations in soil were quantified before and after 60d period. The results indicated that A. elongatum could significantly enhance PYR removal (from 46% to 61%) but had less impact on PHE removal (from 96% to 97%). Plant uptake of the PAHs was insignificant. Biodegradation was the key mechanism of PAH removals (<3% losses in the sterile control). Increase in PMC or Tween 80 levels increased the removal of PYR but not of PHE. Maximal PYR removal of 79% and 92% were observed in vegetated soil receiving 100mgkg(-1) Tween 80 and 7.5% PMC, respectively. Enhanced PYR removal in soil receiving PMC could be explained by the elevated levels of DOC, TOM and microbial populations as suggested by Pearson correlation test. While the positive effect of Tween 80 on PYR removal could probably due to its capacities to enhance PYR bioavailability in soil. This paper suggests that the addition of either PMC or nonionic-surfactant Tween 80 could facilitate phytoremediation of PAH contaminated soil.     

Brassinosteroid alleviates phenanthrene and pyrene phytotoxicity by increasing detoxification activity and photosynthesis in tomato

The present study was carried out to investigate the effects of exogenously applied 24-epibrassinolide (BR) on growth, gas exchange, chlorophyll fluorescence characteristics, lipid peroxidation and antioxidant systems of tomato seedlings grown under different levels (0, 10, 30, 100 and 300 μM) of phenanthrene (PHE) and pyrene (PYR) in hydroponics. A concentration-dependent decrease in growth, photosynthetic pigment contents, net photosynthetic rate (Pn), stomatal conductance (Gs), maximal quantum yield of PSII (Fv/Fm), effective quantum yield of PSII (Φ_PSII), photochemical quenching coefficient (qP) has been observed following PHE and PYR exposure. By contrast, non-photochemical quenching coefficient (NPQ) was increased. PHE was found to induce higher stress than PYR. However, foliar or root application of BR (50 nM and 5 nM, respectively) alleviated all those depressions with a sharp improvement in the activity of photosynthetic machinery. The activities of guaicol peroxidase (GPOD), catalase (CAT), ascorbate peroxidase (APX) and glutathione reductase (GR) as well as content of malondialdehyde (MDA) were increased in a dose-dependent manner under PHE or PYR treatments. Compared with control the highest increments of GPOD, CAT, APX, GR and MDA by PHE/PYR alone treatments were observed following 300 μM concentration, which were 67%, 87%, 53%, 95% and 74% by PHE and 42%, 53%, 30%, 86% and 62% by PYR, respectively. In addition, both reduced glutathione (GSH) and oxidized glutathione (GSSG) were induced by PHE or PYR. Interestingly, BR application in either form further increased enzymatic and non enzymatic antioxidants in tomato roots treated with PHE or PYR. Our results suggest that BR has an anti-stress effect on tomato seedlings contaminated with PHE or PYR and this effect is mainly attributed by increased detoxification activity.     

PAH-sequestration capacity of granular and powder activated carbon amendments in soil, and their effects on earthworms and plants

A field lysimeter study was carried out to investigate whether the amendment of 2% powder and granular activated carbon (PAC and GAC) to a soil with moderate PAH contamination had an impact on the PAH bioaccumulation of earthworms and plants, since AC is known to be a strong sorbent for organic pollutants. Furthermore, secondary effects of AC on plants and earthworms were studied through growth and nutrient uptake, and survival and weight gain. Additionally, the effect of AC amendments on soil characteristics like pH, water holding capacity, and the water retention curve of the soil were investigated. Results show that the amendment of 2% PAC had a negative effect on plant growth while the GAC increased the growth rate of plants. PAC was toxic to earthworms, demonstrated by a significant weight loss, while the results for GAC were less clear due to ambiguous results of a field and a parallel laboratory study. Both kinds of AC significantly reduced biota to soil accumulation factors (BSAFs) of PAHs in earthworms and plants. The GAC reduced the BSAFs of earthworms by an average of 47 ± 44% and the PAC amendment reduced them by 72 ± 19%. For the investigated plants the BSAFs were reduced by 46 ± 36% and 53 ± 22% by the GAC and PAC, respectively.     

Biodegradability of aged pyrene and phenanthrene in a natural soil

A study was conducted to evaluate the biodegradability of pyrene (PYR) and phenanthrene (PHE) aged in a natural soil. Both the single and binary systems were either biostimulated via a nutrient amendment or bioaugmented via an inoculation of the enriched bacteria and nutrients. Aging resulted in higher concentration of both compounds and smaller bacterial activity in the solution-phase. Surprisingly, the total biodegraded extent was greater in the aged soil system than in the freshly spiked system. As anticipated, biostimulation was not appropriate to attain an effective biodegradation in this study, and bioaugmentation achieved a substantial increase the total biodegradation extent. The above findings were attributed to indigenous Pseudomonas aeruginosa entering a stationary-phase during the 200-day aging and producing rhamnolipid biosurfactants. In addition, a different sampling technique (i.e., after vigorous hand-shaking) revealed a 15 times higher microbial population than the normal sampling from the stagnant solution. Therefore, PAH bioavailability in the aged soils can be underestimated when the microbial activity is determined only from the stagnant solution. Furthermore, cometabolism enhanced PYR degradation when PHE was present as a primary substrate.     

Bioaccumulation and bioavailability of polybrominated diphynel ethers (PBDEs) in soil

Earthworms were exposed to artificially contaminated soils of DE-71 and DE-79 to investigate the bioaccumulation and bioavailability of PBDEs in soil. All major congeners were bioavailable to earthworms. The uptake and elimination rate coefficients of PBDEs decreased with their logK_ows. The biota soil accumulation factors of PBDEs also declined with logK_ow. These may be due to the large molecular size and the high affinity of PBDEs to soil particles. The concentrations extracted by Tenax for 6 h correlated very well with those found in earthworms, suggesting that the bioavailability of PBDEs in soil is related to the fraction of rapid desorption from soil. This also indicates that 6 h Tenax extraction is a good proxy for the bioavailability of PBDEs to earthworms in soil. The BSAFs of PBDEs in aged soil decreased 22-84% compared to freshly spiked soil, indicating that aging may diminish the bioavailability of PBDEs in soil significantly.     

Chemical assays of availability to earthworms of polycyclic aromatic hydrocarbons in soil

The bioavailable concentration of an organic pollutant is less than the concentration determined by vigorous extraction of soil. Because bioavailability varies with the particular compound, soil, and aging time, an assay for bioavailability is needed. Three methods were tested: extraction with a 25% aqueous solution of tetrahydrofuran (THF), 95% ethanol, and C18 membranes. Evaluations were conducted with a mixture of four polycyclic aromatic hydrocarbons (PAHs) added to five dissimilar soils and with pyrene as sole PAH added to six soils, and the availability of aged and freshly added compounds was determined. Assimilation by earthworms (Eisenia fetida) was used to assess bioavailability. For extraction with THF and earthworm uptake, the correlation coefficients of determination (R2) for anthracene, chrysene, pyrene, and benzo(a)pyrene added as a mixture exceeded 0.85. The R2 values for assays with the C18 membrane were 0.77 or higher. The values for pyrene added alone were 0.710 and 0.823, respectively. R2 values for assays with ethanol often exceeded 0.87, but lower values were sometimes obtained. We suggest that such solvent or solid-phase extractions may be useful in assessing PAH bioavailability.     

Predicting bioavailability of PAHs in field-contaminated soils by passive sampling with triolein embedded cellulose acetate membranes

Triolein embedded cellulose acetate membrane (TECAM) was used for passive sampling of the fraction of naphthalene, phenanthrene, pyrene and benzo[a]pyrene in 18 field-contaminated soils. The sampling process of PAHs by TECAM fitted well with a first-order kinetics model and PAHs reached 95% of equilibrium in TECAM within 20 h. Concentrations of PAHs in TECAM (C_TECAM) correlated well with the concentrations in soils (r² = 0.693-0.962, p < 0.001). Furthermore, concentrations of PAHs determined in the soil solution were very close to the values estimated by C_TECAM and the partition coefficient between TECAM and water (K_TECAM-w). After lipid normalization nearly 1:1 relationships were observed between PAH concentrations in TECAMs and earthworms exposed to the soils (r² = 0.591-0.824, n = 18, p < 0.01). These results suggest that TECAM can be a useful tool to predict bioavailability of PAHs in field-contaminated soils.     

Bioremediation of tributyltin contaminated sediment: degradation enhancement and improvement of bioavailability to promote treatment processes

Bioremediation of tributyltin (TBT) contaminated sediment was studied and degradation enhancement and improvement of bioavailability were also investigated. In TBT spiked sediment, the half-life of TBT in the control sample, representing natural attenuation, was 578 d indicating its persistence. In the stimulated sample (pH 7.5, aeration and incubated at 28 °C), the half-life was significantly reduced to 11 d. Further stimulation by nutrient addition (succinate, glycerol and l-arginine) or inoculation with Enterobacter cloacae (∼10⁷ viable cells g⁻¹ of sediment) resulted in half-life reduction to 9 and 10 d, respectively. In non-spiked sediment, the indigenous microorganisms were able to degrade aged TBT, but the extended period of contamination decreased the degradation efficiency. To improve bioavailability, addition of surfactant, adjustment of salinity and sonication were studied. The highest percentage solubilisation of TBT in water was obtained by adjusting salinity to 20 psu, which increased the solubility of TBT from 13% to 33%. Half-lives after bioavailability was improved were 5, 4 and 4 d for stimulation, stimulation w/nutrient addition and stimulation w/inoculation, respectively. However, natural attenuation in the control sample was not enhanced. The results show that providing suitable conditions is important in enhancing TBT biodegradation, and bioavailability improvement additionally increased the rate and degraded amount of TBT. Unfortunately, nutrient addition and inoculation of the degrader did not enhance the degradation appreciably.     

Enhancement of chlorophenol sorption on soil by geophagous earthworms (Metaphire guillelmi)

Earthworms are the dominant soil biomass of many terrestrial ecosystems and markedly influence the physico-chemical and biological properties of soil; however, little is known about the effects of earthworm activities on the environmental behavior of micropollutants in soil. We studied the sorption and desorption of 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol on geophagous earthworm (anecic Metaphire guillelmi) casts of various aging times and on the parent soil. The casts were characteristic of lower pH and higher content of fine particles (silt and clay) than the parent soil. The sorption of the chlorophenols on the soil and casts were well fitted to linear isotherms, with sorption capacity in the order of pentachlorophenol > 2,4-dichlorophenol > 2,4,6-trichlorophenol. The sorption on the cast with different aging time was quite similar and was higher than on the parent soil. The sorption on the soil did not change between pH 7.07 of the soil and pH 6.76 of the casts. The desorption hysteresis of the chlorophenols on the soil and casts was compound specific and 2,4,6-trichlorophenol showed the highest hysteresis. The higher sorption capacity of the casts was not owing to the lowered pH of the casts, but mainly to the higher fine particles in the casts and the possible changes of nature of the soil organic matter through the earthworm gut passage. Our results indicate that geophagous earthworms may change sorption behavior and thus the bioavailability and transport of chlorophenols in soil. Earthworm effects should be considered when evaluating the environmental behavior and risk of organic pollutants in the ecosystems where earthworms are abundant.     

Dissipation gradients of phenanthrene and pyrene in the Rice rhizosphere

An experiment was conducted to reveal the effects of rice cultivation as well as polycyclic aromatic carbohydrates (PAHs) degrading bacterium (Acinetobacter sp.) on the dissipation gradients of two PAHs (PHE and PYR) in the rhizosphere. The results showed that the presence of rice root and bacteria significantly accelerated the dissipation rate of PHE and PYR. The root exudates contributed to the formation of dissipation gradients of PHE and PYR along the vertical direction of roots, with a higher dissipation rate in the rhizosphere and near rhizosphere zone than the soil far away the rhizosphere.     

Butanol extraction to predict bioavailability of PAHs in soil

The feasibility of a mild-solvent extraction procedure to predict the bioavailability of individual polycyclic aromatic hydrocarbons (PAHs) in soil was assessed. The quantities that were degraded during the course of biodegradation of phenanthrene and pyrene in soil with or without plants correlated with the amounts extracted by n-butanol, with R2 values of 0.971 and 0.994, respectively. Six consecutive groups of earthworms removed ca. 70% of the pyrene remaining after extensive biodegradation, a value similar to the quantity extracted by n-butanol. The amount of chrysene aged in sterilized soil that was extracted by n-butanol was not statistically different from the quantities assimilated by earth-worms (Eisenia fetida) introduced into the soil. Such a mild extraction procedure may be useful as a means of predicting PAH bioavailability.     

Effects of biochar and the earthworm Eisenia fetida on the bioavailability of polycyclic aromatic hydrocarbons and potentially toxic elements

Polycyclic aromatic hydrocarbons (PAHs) and potentially toxic elements (PTEs) were monitored over 56 days in calcareous contaminated-soil amended with either or both biochar and Eisenia fetida. Biochar reduced total (449 to 306 mg kg⁻¹) and bioavailable (cyclodextrin extractable) (276 to 182 mg kg⁻¹) PAHs, PAH concentrations in E. fetida (up to 45%) but also earthworm weight. Earthworms increased PAH bioavailability by >40%. Combined treatment results were similar to the biochar-only treatment. Earthworms increased water soluble Co (3.4 to 29.2 mg kg⁻¹), Cu (60.0 to 120.1 mg kg⁻¹) and Ni (31.7 to 83.0 mg kg⁻¹) but not As, Cd, Pb or Zn; biochar reduced water soluble Cu (60 to 37 mg kg⁻¹). Combined treatment results were similar to the biochar-only treatment but gave a greater reduction in As and Cd mobility. Biochar has contaminated land remediation potential, but its long-term impact on contaminants and soil biota needs to be assessed.     

Is black carbon a better predictor of polycyclic aromatic hydrocarbon distribution in soils than total organic carbon?

Black carbon (BC) and total organic carbon (TOC) were quantified in the surface soils of Switzerland (N = 105) and Delhi (N = 36), India, to examine their relationships with contents of polycyclic aromatic hydrocarbons (PAH). BC content in Swiss (background) soils (N = 104) varied from 0.41 to 4.75 mg/g (median: 1.13 mg/g) and constituted 1-9% (median: 3%) of TOC. Indian (urban) soils had similar BC concentrations (0.37-2.05 mg/g, median: 1.19 mg/g), with relatively higher BC/TOC (6-23%, median: 13%). Similar to TOC, BC showed significant positive correlation with lighter PAH, but no correlation with heavier PAH in Swiss soils. In contrast, heavier PAH were significantly correlated only with BC in Delhi soils. It seems that TOC governs the distribution of PAH in organic matter rich background soils, while the proximity to emission sources is reflected by BC-PAH association in urban soils.     

Sorption comparison between phenanthrene and its degradation intermediates, 9,10-phenanthrenequinone and 9-phenanthrol in soils/sediments

The degradation intermediates of phenanthrene (PHE) may have increased health risks to organisms than PHE. Therefore, environmental fate and risk assessment studies should take into considerations of PHE degradation products. This study compared the sorption properties of PHE and its degradation intermediates, 9,10-phenanthrenequinone (PQN) and 9-phenanthrol (PTR) in soils, sediments and soil components. A relationship between organic carbon content (f_OC) and single-point sorption coefficient (log K_d) was observed for all three chemicals in 10 soils/sediments. The large intercept in the log f_OC − log K_d regression for PTR indicated that inorganic fractions control PTR sorption in soils/sediments. No relationship between specific surface area and K_d was observed. This result indicated that determination of surface area based on gas sorption could not identify surface properties for PHE, PQN, and PTR sorption and thus provide limit information on sorption mechanisms. The high sorption and strong nonlinearity (low n values) of PTR in comparison to PHE suggested that the mobility of PTR could be lower than PHE. Increased mobility of PQN compared with PHE may be expected in soils/sediments because of PQN lower sorption. The varied sorption properties of the three chemicals suggested that their environmental risks should be assessed differently.     

Determination of polycyclic aromatic hydrocarbons in urban street dust: implications for human health

The determination of sixteen polycyclic aromatic hydrocarbons in urban street dust has been done. Samples were collected from 12 sampling locations in a city centre location (Newcastle upon Tyne, north east England) and extracted using in situ pressurised fluid extraction followed by gas chromatography mass spectrometry. From the results it was possible to identify three groups, with respect to PAH concentration, with PAH contents ranging between 0.6-2.3 mg kg⁻¹, 15.6-22.5 mg kg⁻¹ and 36.1-46.0 mg kg⁻¹. The total PAH content of samples from these sampling sites has been compared to 22 urban locations around the world; comparable levels were found in these samples compared to the other cities around the world.The potential source of PAHs has been investigated by investigating the proportion of pyrogenic and petrogenic material in urban street dust using specific individual PAH ratios. The results indicate that the PAH content of urban street dust from the chosen sites are more likely to be due to pyrogenic sources i.e. vehicle exhaust emissions. The particle size fractions (<63 μm; 63-125 μm; 125-250 μm; 250-500 μm; 500-1000 μm; and 1000-2000 μm) of individual PAHs in three selected sampling sites was investigated. In two of the selected sites the PAH content was independent of particle size whereas in sampling site 10 elevated PAH levels are noted in the <63 μm size fraction. Sampling site 10 is located at the junction of three road tributaries which are used as major access points to the east of the city centre. Finally, the potential health risk for unintentional consumption of PAHs was assessed in terms of a mean daily intake (based on an ingestion rate of 100 mg d⁻¹). It was found that all 4-6 membered ring PAHs had concentrations in excess of the mean daily intake thereby reflecting a potential health risk, particularly in the smallest size particle fractions.     

Effect of external iron and arsenic species on chelant-enhanced iron bioavailability and arsenic uptake in rice (Oryza sativa L.)

This study was conducted to investigate the effect of external iron status and arsenic species on chelant-enhanced iron bioavailability and arsenic uptake. Rice seedlings (Oryza sativa L.) were used as model plant, and were grown in artificially contaminated sandy soils irrigated with Murashige and Skoog (MS) culture solution. Arsenate uptake in roots and shoots of rice seedlings were affected significantly (p > 0.05) while dimethylarsinic acid (DMAA) was not by the additional iron and chelating ligand treatments. Regardless of iron concentrations in the soil solution, HIDS increased arsenic uptake for roots more than EDTA and EDDS. Chelating ligands and arsenic species also influenced iron uptake in rice roots. Irrespective of arsenic species, HIDS was found to be more effective in the increase of iron bioavailability and uptake in rice roots compared to other chelants. There was a significant positive correlation (r = 0.78, p < 0.05) between arsenate and iron concentrations in the roots of rice seedlings grown with or without additional iron indicating that arsenate inhibit iron uptake. In contrast, there was no correlation between iron and DMAA uptake in roots. Poor correlation between iron and arsenic in shoots indicated that iron uptake in shoots was neither affected by additional iron nor by arsenic species. Compared to the control, chelating ligands increased iron uptake in shoots of rice seedlings significantly (p < 0.05). Regardless of additional iron and arsenic species, iron uptake in rice shoots did not differed among EDTA, EDDS, and HIDS treatments.     

Using deuterated PAH amendments to validate chemical extraction methods to predict PAH bioavailability in soils

Validating chemical methods to predict bioavailable fractions of polycyclic aromatic hydrocarbons (PAHs) by comparison with accumulation bioassays is problematic. Concentrations accumulated in soil organisms not only depend on the bioavailable fraction but also on contaminant properties. A historically contaminated soil was freshly spiked with deuterated PAHs (dPAHs). dPAHs have a similar fate to their respective undeuterated analogues, so chemical methods that give good indications of bioavailability should extract the fresh more readily available dPAHs and historic more recalcitrant PAHs in similar proportions to those in which they are accumulated in the tissues of test organisms. Cyclodextrin and butanol extractions predicted the bioavailable fraction for earthworms (Eisenia fetida) and plants (Lolium multiflorum) better than the exhaustive extraction. The PAHs accumulated by earthworms had a larger dPAH:PAH ratio than that predicted by chemical methods. The isotope ratio method described here provides an effective way of evaluating other chemical methods to predict bioavailability.     

Global DNA methylation in earthworms: a candidate biomarker of epigenetic risks related to the presence of metals/metalloids in terrestrial environments

In this work, possible relationships between global DNA methylation and metal/metalloid concentrations in earthworms have been explored. Direct correlation was observed between soil and tissue As, Se, Sb, Zn, Cu, Mn, Ag, Co, Hg, Pb (p < 0.05). Speciation results obtained for As and Hg hint at the capability of earthworms for conversion of inorganic element forms present in soil to methylated species. Inverse correlation was observed between the percentage of methylated DNA cytosines and total tissue As, As + Hg, As + Hg + Se + Sb (β = −0.8456, p = 0.071; β = −0.9406, p = 0.017; β = −0.9526, p = 0.012 respectively), as well as inorganic As + Hg (β = −0.8807, p = 0.049). It was concluded that earthworms would be particularly helpful as bioindicators of elements undergoing in vivo methylation and might also be used to assess the related risk of epigenetic changes in DNA methylation.     

Combined effects of DOM and biosurfactant enhanced biodegradation of polycylic armotic hydrocarbons (PAHs) in soil–water systems

This study systematically investigated the interactive effects of dissolved organic matter (DOM) and biosurfactant (rhamnolipid) on the biodegradation of phenanthrene (PHE) and pyrene (PYR) in soil–water systems. The degradations of two polycyclic aromatic hydrocarbons (PAHs) were fitted well with first order kinetic model and the degradation rates were in proportion to the concentration of biosurfactant. In addition, the degradation enhancement of PHE was higher than that of PYR. The addition of soil DOM itself at an environmental level would inhibit the biodegradation of PAHs. However, in the system with co-existence of DOM and biosurfactant, the degradation of PAHs was higher than that in only biosurfactant addition system, which may be attributed to the formation of DOM–biosurfactant complex micelles. Furthermore, under the combined conditions, the degradation of PAH increased with the biosurfactant concentration, and the soil DOM added system showed slightly higher degradation than the compost DOM added system, indicating that the chemical structure and composition of DOM would also affect the bioavailability of PAHs. The study result may broaden knowledge of biosurfactant enhanced bioremediation of PAHs contaminated soil and groundwater.     

Cu fractions, mobility and bioavailability in soil-wheat system after Cu-enriched livestock manure applications

Fertilization of crops with livestock manure (LM) is a common waste disposal option, but repeated application of LM containing high concentrations of heavy metals such as Cu could lead to crop toxicity and environmental risk. To examine the Cu availability and uptake by wheat in a Mollisol affected by Cu-enriched LM, pot experiments were conducted. LM (376 mg kg⁻¹ Cu originally) was spiked with different concentrations of Cu (0, 100, 200, 400, 600 and 800 mg kg⁻¹ soil, added as CuSO₄) to simulate soil Cu contamination by LM application. The results indicated that Cu was predominately distributed in organic bound fraction, while the most drastic increase was found in reducible fraction. Acid-extractable fraction played a more important role than other fractions in controlling the mobility and bioavailability of Cu. DTPA-extractable Cu may overestimate the Cu bioavailability since DTPA solution could extract soluble and part of stable forms. The application of LM at 1% level significantly decline the Cu mobility, but that at 3% level exhibited the opposite effect.Although the quantities of Cu in wheat was very low compared with the accumulation in soil, Cu concentrations in roots increased evidently from 12 to 533 mg kg⁻¹ and that in aerial parts were in a narrow range from 12.1 to 32.7 mg kg⁻¹, indicating the more sensitivity of roots to the Cu toxicity. The Cu concentrations in grains after 3% manure application did not approach the threshold for Cu toxicity (<20 mg kg⁻¹) even at higher Cu addition rates.