Anaerobic PAH degradation in soil by a mixed bacterial consortium under denitrifying conditions

Polycyclic aromatic hydrocarbons (PAHs) are one of the main classes of contaminants in the terrestrial environment. Concentrations of biphenyl, fluorene, phenanthrene and pyrene were added to soil samples in order to investigate the anaerobic degradation potential of PAHs under denitrifying conditions. A mixed population of microorganisms obtained from a paddy soil was incubated for 20 days in anaerobic conditions in the presence of soil alone or with nitrate, adding, as electron donors, PAHs and, in some samples, glucose or acetate. At regular time intervals oxidation-reduction potential, PAHs concentration, microbial ATP and nitrate concentration into the solution were measured. Degradation trends for each hydrocarbon are similar under all conditions, indicating that the molecular conformation prevails over other parameters in controlling the degradation. Poor degradation results were obtained when PAHs were the only organic matter available for the inoculum, thus confirming the recalcitrance to degradation of these compounds. Biodegradation was influenced by the addition of other carbon sources. As better degradation results were generally obtained when acetate or glucose were added, the hypothesis of a co-metabolic enhancement of PAH biodegradation seems likely. Thus, anaerobic biodegradation of PAHs studied, biphenyl, fluorene, phenanthrene and pyrene, seems to be possible both through fermentative and respiratory metabolism, provided that low molecular weight co-metabolites and suitable electron acceptors (nitrate) are present.     

Changing contaminant mobility in a dredged canal sediment during a three-year phytoremediation trial

Metal mobility and degradation of organic pollutants were investigated in a contaminated canal sediment in NW England. Sediment was dredged and exposed above the water surface, planted with multiple taxa of Salix, Populus and Alnus and monitored over 32 months. Short-term metal fractionation and phytotoxicity during sediment oxidation were also evaluated in separate laboratory studies. Zinc and Pb redistributed into more mobile fractions, which increased toxicity of the sediment to plants in the laboratory. In contrast, at the canal site, mobility of most elements decreased and total concentrations of Zn, Pb, Cu and Cd fell. Petroleum hydrocarbon concentrations decreased, but the tree-planted treatments appeared less effective at reducing PAH concentrations than treatments colonised by invasive plants. Tree survivorship decreased over time, suggesting increasing phytotoxicity of the exposed sediment in the longer term. Trees provided little benefit in terms of sediment remediation. Options for future management of the sediment are evaluated.     

Immobilization of fungal laccase onto a nonionic surfactant-modified clay material: application to PAH degradation

Nonionic surfactant-modified clay is a useful absorbent material that effectively removes hydrophobic organic compounds from soil/groundwater. We developed a novel material by applying an immobilized fungal laccase onto nonionic surfactant-modified clay. Low-water-solubility polycyclic aromatic hydrocarbons (PAHs) (naphthalene/phenanthrene) were degraded in the presence of this bioactive material. PAH degradation by free laccase was higher than degradation by immobilized laccase when the surfactant concentration was allowed to form micelles. PAH degradation by immobilized laccase on TX-100-modified clay was higher than on Brij35-modified clay. Strong laccase degradation of PAH can be maintained by adding surfactant monomers or micelles. The physical adsorption of nonionic surfactants onto clay plays an important role in PAH degradation by laccase, which can be explained by the structure and molecular interactions of the surfactant with the clay and enzyme. A system where laccase is immobilized onto TX-100-monomer-modified clay is a good candidate bioactive material for in situ PAHs bioremediation.     

Influence of pH on the sonolysis of ciprofloxacin: Biodegradability, ecotoxicity and antibiotic activity of its degradation products

The presence of antibiotics in the aquatic environment has raised concerns due to the potential risk for the emergence or persistence of antibiotic resistance. Antibiotics are often poorly degraded in conventional wastewater treatment plants. In this study, sonolysis at 520 kHz and 92 W L⁻¹ was used for the degradation of the fluoroquinolone antibiotic ciprofloxacin. In a first experiment at pH 7, 57% of the ciprofloxacin (15 mg L⁻¹) was degraded after 120 min of ultrasonic irradiation at 25 °C. pH proved to be an important parameter determining the degradation rate, since the pseudo first order degradation constant increased almost fourfold when comparing treatment at pH 7 (0.0058 min⁻¹) and pH 10 (0.0069 min⁻¹) with that at pH 3 (0.021 min⁻¹). This effect can be attributed to the degree of protonation of the ciprofloxacin molecule. The BOD/COD ratio of the solutions, which is a measure for their biodegradability, increased from 0.06 to 0.60, 0.17, and 0.18 after 120 min of irradiation depending on the pH (3, 7, and 10, respectively). The solution treated at pH 3 can even be considered readily biodegradable (BOD/COD > 0.4). The antibiotic activity against Escherichia coli (G−) and Bacillus coagulans (G+) of the treated solutions also reduced after sonolysis. The highest decrease was again found when irradiated at pH 3. In contrast, ecotoxicity of the solutions to the alga Pseudokirchneriella subcapitata increased 3- to 10-fold after 20 min of treatment, suggesting the formation of toxic degradation products. The toxicity slowly diminished during further treatment.     

The effects of aging time on the fraction distribution and bioavailability of PAH

Understanding the effects of aging time on the fraction distribution and bioavailability of PAH, such as phenanthrene (PHE) and pyrene (PYR), has considerable benefits for risk assessment, food security and remediation strategies for contaminated soil. The results of the present study show that the proportion of the desorbed PHE decreased from ca. 82% at day 0 to ca. 65% at day 150. In addition, non-desorbed PHE increased from ca. 18% at day 0 to ca. 31% at day 150, whereas the changes of desorbed and non-desorbed PYR showed no significant trend during this aging period. The proportion of desorbed PYR was lower than that of PHE, whereas the opposite occurred with the non-desorbed fraction. After 150 d of aging, the proportion of bound residues (PHE and PYR) increased significantly with the cultivating time from ca. 0.2% to ca. 4.7% and ca. 0.1% to ca. 1.2% for PHE and PYR, respectively. In addition, the bioavailability of PAH (PHE and PYR) to earthworms was also assessed over 0-150 d. The results showed that the uptake rate and bioconcentration factor (BCF) of pollutants by earthworms displayed the following biphasic character: a rapid decrease over the first 15 d followed by a slow decrease over the next 135 d. Moreover, the earthworm uptake rate of PHE was greater than that of PYR throughout the incubation period, indicating that PHE has a higher bioavailability than PYR. In addition, the positive correlation between the uptake rate of earthworms and PAH extractability suggested that a three-step extraction is a reliable approach to predict PHE bioavailability in soil. However, a limit was observed for PYR.     

Modelling of an enhanced PAH attenuation experiment and associated biogeochemical changes at a former gasworks site in southern Germany

Former manufactured gas plant sites often form a widespread contaminant source in the subsurface, leading to large plumes that contain a wide variety of tar-oil related compounds. Although most of these compounds eventually degrade naturally, the relevant processes tend to be slow and inefficient, often leaving active remediation as the only viable option to eliminate the risks of toxic substances to reach potential receptors such as surface waters or drinking water wells. In this study we use a reactive transport model to analyse the fate of a contaminant plume containing acenaphthene, methylbenzofurans and dimethylbenzofurans (i) prior to the installation of an active remediation scheme and (ii) for an enhanced remediation experiment during which O(2) and H(2)O(2) were added to the contaminated groundwater through a recirculation well. The numerical model developed for this study considers the primary contaminant degradation reactions (i.e., microbially mediated redox reactions) as well as secondary and competing mineral precipitation/dissolution reactions that affect the site's hydrochemistry and/or contaminant fate. The model was calibrated using a variety of constraints to test the uncertainty on model predictions resulting from the undocumented presence of reductants such as pyrite. The results highlight the important role of reactive transport modelling for the development of a comprehensive process understanding.     

Effects of anthracene, pyrene and benzo[a]pyrene spiking and sewage sludge compost amendment on soil ecotoxicity during a bioremediation process

The fate of spiked anthracene, pyrene and benzo[a]pyrene in soil with or without sewage sludge compost was assessed during a 6-month bioremediation process simulating landfarming. Bioassays and physico-chemical analyses were employed to monitor toxicity change in soil samples and elutriates through ten sampling campaigns. Pearson product-moment correlation coefficient was determined to measure the strength of relationship between bioassays and physico-chemical analyses. The PAH dissipation in soil was enhanced after the first water addition, and the remaining amounts at the end of the experiment were positively correlated to the number of benzene rings and the presence of sewage sludge compost. Toxicity of soil elutriates to Daphnia magna was evident at early stages, originating exclusively from sewage sludge compost amendment. The lettuce root elongation was continuously inhibited by elutriates for all the treatments including control soil, probably due to high salinity or to unaddressed leachable phytotoxic compounds that were present in the experimental soil. The newly developed direct solid-phase chronic toxicity test using ostracod (Heterocypris incongruens) succeeded in evaluating the soil-bound PAH toxicity, as PAHs could not be detected in elutriates.     

Deltamethrin degradation and effects on soil microbial activity

Deltamethrin [(S)-cyano-3-phenoxybenzyl-cis-(1R,3R)-2,2-dimethyl) cyclo–propane carboxylate),1] labelled at gem-dimethyl groups of the cyclopropane ring was applied on two Egyptian soils at a level of 10 mg/kg soil for a laboratory incubation experiment under aerobic and anaerobic conditions. A steady decrease of soil extractable¹⁴C-residues, accompanied by a corresponding increase of non- extractable bound ¹⁴C-residues was observed over a 90-day incubation period. The percentage of evolved ¹⁴CO₂ increased with time under aerobic and anaerobic conditions in both soils. The effect of deltamethrin on soil microorganisms as well as the counter effect of microorganisms on the insecticide was also investigated. As the incubation period increased, the inhibitory effect of the insecticide on the microorganisms decreased and the evolution of carbon dioxide depended on the applied dose. The nature of soil methanol soluble residues was determined by chromatographic analysis which revealed the presence of the parent insecticide as the main product in addition to four metabolites: 3-(2′,2′-dibromovinyl)-2,2-dimethylcyclopropane carboxylic acid (II); 3-phenoxybenzaldehyde (III); 3-phenoxybenzoic acid (IV); 3-phenoxybenzyl alcohol (V).     

Assessment of the effects of soil PAH accumulation by a battery of ecotoxicological tests

Surface soils were collected at remote, urban and industrial sites in the Southern of Italy in order to evaluate PAH concentrations and assess the toxic effects by a battery of ecotoxicological tests. The tests were performed on whole soils and on both organic and aqueous extracts. Further goal of this study was to integrate the results coming from each test and matrix in a synthetic toxicity index. The highest summation sigmaPAH concentrations were measured at the industrial soil, although this one did not show an high ecotoxicological risk. Among the performed tests, the phytotoxicity tests showed the highest sensitivity. For whole soil, the worst case always has been represented by test through bacteria. Our results could represent the first step toward the selection of a proper battery to characterize the soil ecotoxicological risk.     

Correlations between PAH bioavailability,degrading bacteria,and soil characteristics during PAH biodegradation in five diffusely contaminated dissimilar soils

The natural biodegradation of seven polycyclic aromatic hydrocarbons (PAHs) by native microorganisms was studied in five soils from Normandy (France) from diffusely polluted areas, which can also pose a problem in terms of surfaces and amounts of contaminated soils. Bioavailability tests using cyclodextrin-based extractions were performed. The natural degradation of low molecular weight (LMW) PAHs was not strongly correlated to their bioavailability due to their sorption to geosorbents. Conversely, the very low degradation of high molecular weight (HMW) PAHs was partly correlated to their poor availability, due to their sorption on complexes of organic matter and kaolinites or smectites. A principal component analysis allowed us to distinguish between the respective degradation behaviors of LMW and HMW PAHs. LMW PAHs were degraded in less than 2–3 months and were strongly influenced by the relative percentage of phenanthrene-degrading bacteria over total bacteria in soils. HMW PAHs were not significantly degraded, not only because they were less bioavailable but also because of a lack of degrading microorganisms. Benzo[a]pyrene stood apart since it was partly degraded in acidic soils, probably because of a catabolic cooperation between bacteria and fungi.     

Negative effects of humic acid addition on phytoremediation of pyrene-contaminated sediments by mangrove seedlings

Vegetated (with Kandelia candel seedlings) and non-vegetated mangrove microcosms were employed to remove pyrene from contaminated sediments, and the effects of adding 6.7% humic acid (HA) on such removal were investigated. At the end of 6-month treatment, residual pyrene concentrations in surface sediments (0-2 cm) of the contaminated microcosms reduced from an initial 5.82 to 0.63 microg g(-1) dw, and the reduction was less in HA amended microcosms with the residual pyrene concentration remained at 3.12 microg g(-1) dw. The pyrene removal percentages in microcosms with HA amendment were 29% for surface aerobic sediments and 41% for bottom (anaerobic) sediments, while the respective removal percentages in microcosms without HA amendment were 89% (surface sediments) and 53% (bottom sediments). Microcosms planted with K. candel seedlings had a significantly higher pyrene removal when compared to the non-vegetated ones, and the average removal percentages were 70.9% and 61.4%, respectively. However, when humic acid was added, no significant difference was found between vegetated and non-vegetated microcosms in pyrene removal, both had less than 40% removal, probably because plant growth in humic acid amended contaminated microcosms, in terms of total biomass, was reduced by 50%. Roots of K. candel could accumulate pyrene from contaminated microcosms, and pyrene concentrations in roots harvested from microcosms with and without humic acid addition were 6.01 and 3.46 microg g(-1) dw, respectively. These results suggest that the addition of HA to contaminated sediments decreased the mangrove microcosm's ability to remove pyrene as pyrene was more tightly bound to the organic matter and plant growth was reduced.     

紫外光助O3、H2O2氧化降解炼油废碱水的可行性实验

炼油高浓度有机废碱水是石化行业中很难降解的废水.本实验用光化学氧化技术对其进行了降解研究,比较了紫外光/空气、紫外光/O3、紫外光/空气/H2O2系统的处理效果.结果表明,光化学氧化技术降解此废水是可行的,紫外光可使废水中COD、油、酚的降解率明显提高.当废水中O3的投加量每小时为22 mg/L,或H2O2投加量为1%/L时,UV/O3法与UV/空气/H2O2法的降解效果相近.同时,通过控制O3浓度或H2O2的投加量等条件,可使废水中COD、油、酚和硫化物降解到地方污染物二级排放标准.     

Acute and chronic ecotoxicity of carbaryl with a battery of aquatic bioassays

The ecotoxic effects of carbaryl (carbamate insecticide) were investigated with a battery of four aquatic bioassays. The nominal effective concentrations immobilizing 50% of Daphnia magna (EC50) after 24 and 48 h were 12.76 and 7.47 µg L^?1, respectively. After 21 days of exposure of D. magna, LOECs (lowest observed effect concentrations) for cumulative molts and the number of neonates per surviving adult were observed at carbaryl concentration of 0.4 µg L^?1. An increase of embryo deformities (curved or unextended shell spines) was observed at 1.8 and 3.7 µg L^?1, revealing that carbaryl could act as an endocrine disruptor in D. magna. Other bioassays of the tested battery were less sensitive: the IC50-72h and IC10-72h of the algae Pseudokirchneriella subcapitata were 5.96 and 2.87 mg L^?1, respectively. The LC50-6d of the ostracod Heterocypris incongruens was 4.84 mg L^?1. A growth inhibition of H. incongruens was registered after carbaryl exposure and the IC20-6d was 1.29 mg L^?1. Our results suggest that the daphnid test sensitivity was better than other used tests. Moreover, carbaryl has harmful and toxic effects on tested species because it acts at low concentrations on diverse life history traits of species and induce embryo deformities in crustaceans.     

Modelling of geochemical and isotopic changes in a column experiment for degradation of TCE by zero-valent iron

Zero-valent iron (ZVI) permeable-reactive barriers have become an increasingly used remediation option for the in situ removal of various organic and inorganic chemicals from contaminated groundwater. In the present study a process-based numerical model for the transport and reactions of chlorinated hydrocarbon in the presence of ZVI has been developed and applied to analyse a comprehensive data set from laboratory-scale flow-through experiments. The model formulation includes a reaction network for the individual sequential and/or parallel transformation of chlorinated hydrocarbons by ZVI, for the resulting geochemical changes such as mineral precipitation, and for the carbon isotope fractionation that occurs during each of the transformation reactions of the organic compounds. The isotopic fractionation was modelled by formulating separate reaction networks for lighter ((12)C) and heavier ((13)C) isotopes. The simulation of a column experiment involving the parallel degradation of TCE by hydrogenolysis and beta-elimination can conclusively reproduce the observed concentration profiles of all collected organic and inorganic data as well as the observed carbon isotope ratios of TCE and its daughter products.     

Molecular and ultrastructural insights into the earthworm Eisenia fetida of the assessment of ecotoxicity during colistin exposure

Colistin is a peptide antibiotic widely used as a feed additive in animal farming, especially in poultry and swine production, for treatment and prevention of gram-negative bacterial infections, as well as for growth promotion use. When orally ingested, colistin is poorly absorbed and is eliminated almost unaltered by the enteric canal into the environment. Thus, risk of environmental toxicity cannot be ignored. In the present study, we examined the effects of colistin on Heath Shock Protein (HSP) 70, metallothionein (MT) gene expressions, and the ultrastructure of intestinal cells, following treatment of the soil indicator earthworm Eisenia fetida with 10, 20, and 100 mg/kg colistin for 7, 14, and 21 days. The results showed that, compared with the control, the expressions of HSP70 and MT genes changed significantly. Colistin caused up-regulations of HSP70’s expression while inhibited the expression of MT gene. In addition, most mitochondria and endoplasmic reticulum were damaged in the group treated with high concentration. The investigation of gene expressions of HSP70 and MT, as well as pathological alterations in the intestinal cells, may provide important information in terms of ecotoxicity of colistin and can be used as early warning system.     

水体铯污染的生物效应与修复植物筛选

研究铯对水生植物的生物效应,筛选对铯富集能力强的水生植物,能够为水体铯污染的修复治理提供方法依据。设计铯污染浓度为0、0.5、2.5和10 mg/L,9种水生植物,3次重复,研究铯对不同水生植物生物效应(BE)和不同水生植物对铯的吸收和富集情况。结果表明,不同植物对水体铯污染有不同的反应。就增加鲜重而言,绿萍、水花生、轮叶狐狸藻、水蓼、水葱增加鲜重大于对照;眼子菜、水葫芦、水稻增加鲜重小于对照;不同植物的铯含量不同。平均铯含量依次为水花生 >水蓼 >水稻 >水葫芦 >水葱 >眼子菜 >轮叶狐狸藻 >绿萍,其中水花生为935.12 mg/kg DW,水蓼为825.93 mg/kg DW,水稻为723.38 mg/kg DW;不同植物清除水体铯污染的能力不同。收获时水体铯浓度降低最多至最少的依次是水蓼、水花生、水稻、轮叶狐狸藻、水葱、水葫芦、绿萍和眼子菜。根据生物效应、植物铯含量、水体铯减少情况,水花生、水蓼、水葫芦和水稻可以作为铯污染水体修复植物。     

热改性坡缕石对土壤镉污染的钝化效果及对土壤镉生态毒性的影响

Cd在土壤中易被农作物吸收和富集,使农作物产量、品质降低,进而造成食品安全威胁。通过钝化实验与盆栽实验,研究了热改性坡缕石对土壤中重金属Cd的钝化效果与植物富集的影响;并结合重金属生物有效态、修复效率和植物内重金属生物吸收因子对Cd钝化效果和Cd生态毒性进行了评价。结果表明,添加4%热改性坡缕石可显著改善土壤理化性质,使土壤中生物有效态Cd质量分数(DTPA与TCLP提取态)分别由1.34 mg·kg⁻¹(DTPA)和1.29 mg·kg^-1(TCLP)降至0.58 mg·kg⁻¹和0.57 mg·kg⁻¹,同时可促使Cd由酸溶态转化为稳定性较强的可氧化态与残渣态。4%热改性坡缕石处理组,可显著改善玉米幼苗生长状况,使幼苗根长和株高分别增加了37.84%和35.60%,根、茎鲜重分别增加了11.41%和86.12%;同时,亦使生物吸收因子降低了44.00%,提升了土壤修复效率。热改性坡缕石具有规模化应用于土壤重金属污染原位修复的潜力。     

Effect of expandable clays and cometabolism on PAH biodegradability

Pyrene and phenanthrene degradation was examined in both single and binary slurry systems for three different natural soils. It was found that the amount of total expandable clays (smectite and vermiculite) was in a good agreement with the achieved rate and extent of biodegradation. For instance, the intrinsic phenanthrene biodegradation rate was 626 microg/L/day for the soil with the largest expandable clay and 3203 microg/L/day for the soil with the least. Similarly, the smallest total pyrene biodegradation (65%) was found for the soil rich in expandable clays, compared to an 82% pyrene reduction in the soil that had the lowest amount. Mass transfer limitation after compound sorption to the clays was more pronounced for the more hydrophobic pyrene. In the presence of phenanthrene, total pyrene biodegradation increased by 2 to 7% due to cometabolism, while the total phenanthrene biodegradation was only enhanced by 0.5 to 5% in the binary system. This research demonstrated that expandable clays might govern the substrate availability to microorganisms and microbial accessibility to substrates. Therefore, the contribution of organic matter and expandable clays to sorption, desorption and biodegradation should be taken equally into account in order to better understand complex bioremediation issues.