Managed bioremediation of soil contaminated with crude oil soil chemistry and microbial ecology three years later

Analysis of samples taken from three experimental soil lysimeters demonstrated marked long-term effects of managed bioremediation on soil chemistry and on bacterial and fungal communities 3 yr after the application of crude oil or crude oil and fertilizer. The lysimeters were originally used to evaluate the short-term effectiveness of managed (application of fertilizer and water, one lysimeter) vs unmanaged bioremediation (one lysimeter) of Michigan Silurian crude oil compared to one uncontaminated control lysimeter. Three years following the original experiment, five 2-ft-long soil cores were extracted from each lysimeter, each divided into three sections, and the like sections mixed together to form composited soil samples. All subsequent chemical and microbiological analyses were performed on these nine composited samples. Substantial variation was found among the lysimeters for certain soil chemical characteristics (% moisture, pH, total Kjeldahl nitrogen [TKN], ammonia nitrogen [NH₄-N], phosphate phosphorous [PO₄-P], and sulfate [SO₄ ⁻²]). The managed lysimeter had 10% the level of total petroleum hydrocarbons (TPH-IR) found in the unmanaged lysimeter. Assessment of the microbial community was performed for heterotropic bacteria, fungi, and aromatic hydrocarbon-degrading bacteria (toluene, naphthalene, and phenanthrene) by dilution onto solid media. There was little difference in the number of heterotrophic bacteria, in contrast to counts of fungi, which were markedly higher in the contaminated lysimeters. Hydrocarbon-degrading bacteria were elevated in both oil-contaminated lysimeters. In terms of particular hydrocarbons as substrates, phenanthrene degraders were greater in number than naphthalene degraders, which outnumbered toluene degraders. Levels of sulfate-reducing bacteria seem to have been stimulated by hydrocarbon degradation.     

Evaluation of extraction methods for arsenic speciation in polluted soil and rotten ore by HPLC-HG-AFS analysis

Three extraction systems including shaking, ultrasonic and microwave-assisted extraction were evaluated. Water and phosphate buffer were tested for the extraction of arsenic compounds in polluted soil, describing the water-soluble or plant-available fraction. The stabilities and recoveries of various arsenic species indicated that no obvious changes of species occurred during the extraction process. The raw extracts were cleaned up by C₁₈ cartridge before analysis. Having optimized the extraction conditions, the arsenic species in polluted soil and ore from the different pollution sources were extracted by microwave-assisted extraction with 0.5 M phosphate buffer as extractant. Arsenic species were quantitatively determined by high performance liquid chromatography on-line coupled with hydride generation atomic fluorescence spectrometry (HPLC-HG-AFS). As(III) and As(V) were the major arsenic species in the polluted soil samples resulting from irrigation by waste water. As^V was the only form found in the rotten ore sampled in mining area. During the extraction process, the recoveries of spiked As(III), As(V), DMA(V) and MMA(V) were 85.4 ± 7.2%, 80.2 ± 6.7%, 101.6 ± 6.7% and 98.8 ± 9.1%, respectively, showing that most water-soluble arsenic could be measured.     

Changes in fungal and bacterial populations in soil treated with two triorganotin(IV) compounds

The effects of two triorganotin(IV) compounds, diphenylbutyltin bromide (Ph₂BuSnBr) and triphenyltin chloride·triphenylphosphine oxide (Ph₃SnCl·Ph₃PO), on soil bacterial and fungal populations were compared with that of Thiram and the commercial triorganotin fungicide ‘Brestan’ (triphenyltin acetate, Ph₃SnOAc). Soil fungal populations were reduced most by Thiram, then by Ph₃SnCl·Ph₃PO, Ph₂BuSnBr and Ph₃SnOAc, in that order. Following the application of the compounds, there was a marked increase in the bacterial population in soil, the increase being greatest with Thiram and least with Ph₃SnCl·Ph₃PO. The triorganotin(IV) compounds were less harmful to soil fungi than Thiram. In Thiram-treated soil, recolonization was slower than in soil treated with the triorganotin(IV) compounds. More species of fungi were tolerant to and persisted after application of the triorganotin(IV) compounds compared with Thiram. Among the fungi that were tolerant to the triorganotin(IV) compounds were cellulolytic species such as Trichoderma.     

The effect of ionization and CH3 ligand for hydrogen storage in Co‐ and Ni‐based organometallic compounds

Maximum capacities of the hydrogen storage in organometallic compounds consisting of Co and Ni atoms bound to C_mH_m ring (m = 4, 5; capped type) were, respectively, found as 3.48 and 3.49 wt % (Guo et al., Struct Chem, 2009, 20, 1107). Here, we extend this study to structures having a transition metal (TM) inserted in C_mH_m ring (inserted type), having TM located on either a C₄H or a C₅H molecule, and the CH₃ ligand bound to the organometallic compounds. We find that for the CoC₄H₄ and NiC₄H₄ complexes, the capped types are 1.39 eV and 1.41 eV higher in energy than the inserted types, respectively, while the ground states for CoC₅H₅ and NiC₅H₅ complexes are found to be the capped type, which are lower than the inserted types, respectively, by 1.27 eV and 1.31 eV. The maximum capacity of hydrogen storage reached 5.13 wt % for both of CoC₄H(H₂)₃ complex and the inserted‐type CoC₄H₄(H₂)₃ complex with a reasonable binding energy (0.3–1.0 eV per H₂). The positively charged C₄H₄ and C₅H₅ molecules do not only improve the capacity of hydrogen storage but also make all H₂ adsorbing in molecular form and keep the adsorption energy in an ideal range. After adding the CH₃ ligand to the compounds, the average adsorption energy of H₂ decreased to an ideal range 0.61–0.94 eV per H₂ and the stability of the compounds is also improved. Finally, we analyze the HOMO–LUMO gaps and display the kinetic stability when H₂ was added to organometallic compounds. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

长江沿岸某化工园区土壤、底泥中酚类化合物的污染现状

建立了同时测定土壤（底泥）样品中12种酚类化合物的检测方法。采用加速溶剂萃取（ASE）与凝胶渗透色谱（GPC）协同净化进行前处理,气相色谱和质谱联用技术（GC-MS）进行定性定量分析。方法检出限为0.410~13.1 μg/kg（干重）,回收率在70.7%~122%之间,相对标准偏差（RSD）为1.2%~16%。基于上述分析方法研究了长江沿岸某化工园区土壤及长江底泥中12种酚类化合物的污染水平。17个土壤样品和7个底泥样品中除对苯二酚外的11种酚类化合物均有检出。土壤和底泥中酚类污染物总含量范围分别为10.16~30.66 mg/kg和18.00~29.83 mg/kg,平均含量分别为18.26 mg/kg和22.51 mg/kg。土壤和底泥中最主要的酚类污染物为4-硝基苯酚和4-氯-3-甲酚,其次为邻氯对苯二酚、4,6-二硝基邻甲基苯酚和2,4,6-三氯酚。该化工园区周边土壤及长江底泥中12种酚类污染物污染水平较低、环境风险较小。     

Microextraction techniques for the determination of volatile and semivolatile organic compounds from plants: A review

Vegetables and fruits are necessary for human health, and traditional Chinese medicine that uses plant materials can cure diseases. Thus, understanding the composition of plant matrix has gained increased attention in recent years. Since plant matrix is very complex, the extraction, separation and quantitation of these chemicals are challenging.