Phytoremediation of pyrene contaminated soils amended with compost and planted with ryegrass and alfalfa.

Ryegrass (Lolium perenne) and alfalfa (Medicago sativa) were planted in pots to remediate pyrene contaminated quartz sand (as a control group), alluvial and red soils amended with and without compost. The pyrene degradation percentages in quartz sand, alluvial soil, and red soil amended with compost (5%, w/w) and planted with ryegrass and alfalfa for 90 d growth were 98-99% and 97-99%, respectively, while those of pyrene in the corresponding treatments amended without compost but planted with ryegrass and alfalfa were 91-96% and 58-89%, respectively. Further, those of pyrene in the respective treatments amended with and without compost but unplanted were 54-77% and 51-63%, respectively. Pyrene contents in both roots and aboveground parts of ryegrass and alfalfa after 90 d growth in quartz sand and the two soils amended with or without compost were trace amounts. Statistical analyses for the parameters of ryegrass planted in red and alluvial soils including the concentrations of total water-soluble volatile low molecular weight organic acids, microbial population, pyrene degradation percentage, and spiked pyrene concentration show significant correlations at 5% and mostly 1% probability levels, by the analysis of variance. It was thus suggested that the interactions among the consortia of plant root exudates, microorganisms, and amended compost in rhizosphere soils could facilitate bioavailability of pyrene and subsequently enhance its dissipation.

Effect of sunlight irradiation on photocatalytic pyrene degradation in contaminated soils by micro-nano size TiO2.

The enhanced catalytic pyrene degradation in quartz sand and alluvial and red soils by micro-nano size TiO(2) in the presence and absence of sunlight was investigated. The results showed that the synergistic effect of sunlight irradiation and TiO(2) was more efficient on pyrene degradation in quartz sand and red and alluvial soils than the corresponding reaction system without sunlight irradiation. In the presence of sunlight irradiation, the photooxidation (without TiO(2)) of pyrene was very pronounced in alluvial and red soils and especially in quartz sand. However, in the absence of sunlight irradiation, the catalytic pyrene degradation by TiO(2) and the photooxidation (without TiO(2)) of pyrene were almost nil. This implicates that ultra-violet (UV) wavelength range of sunlight plays an important role in TiO(2)-enhanced photocatalytic pyrene degradation and in photooxidation (without TiO(2)) of pyrene. The percentages of photocatalytic pyrene degradation by TiO(2) in quartz sand, alluvial and red soils under sunlight irradiation were 78.3, 23.4, and 31.8%, respectively, at 5h reaction period with a 5% (w/w) dose of the amended catalyst. The sequence of TiO(2)-enhanced catalytic pyrene degradation in quartz sand and alluvial and red soils was quartz sand>red soil>alluvial soil, due to different texture and total organic carbon (TOC) contents of the quartz sand and other two soils. The differential Fourier transform infrared (FT-IR) spectra of degraded pyrene in alluvial soil corroborate that TiO(2)-enhanced photocatalytic degradation rate of degraded pyrene was much greater than photooxidation (without TiO(2)) rate of degraded pyrene. Based on the data obtained, the importance for the application of TiO(2)-enhanced photocatalytic pyrene degradation and associated organic contaminants in contaminated soils was elucidated.

Oxidative degradation of pyrene in contaminated soils by δ-MnO2 with or without sunlight irradiation.

The enhanced oxidative degradation of pyrene in quartz sand and alluvial and red soils by micro-nano size birnessite (δ-MnO(2)) in the presence and absence of sunlight was investigated. The degradation of pyrene by δ-MnO(2) in quartz sand showed very little synergistic effect of sunlight irradiation on δ-MnO(2) oxidizing power. However, pyrene degradation by δ-MnO(2) in alluvial and red soils was greater under solar irradiation than the combination of photooxidation of pyrene and oxidation of pyrene by δ-MnO(2). The oxidative degradation percentages of pyrene by δ-MnO(2) under sunlight irradiation are 94.8, 97.7, and 100% for alluvial soil, red soil, and quartz sand, respectively. Oxidative degradation percentages of pyrene by δ-MnO(2) in alluvial and red soils with irradiation of sunlight almost attained a maximum at 1 h with a 5% (w/w) dose of the amended oxidant. Due to their different total organic carbon (TOC) contents, the sequence of enhanced oxidative degradation of pyrene by δ-MnO(2) in quartz sand and alluvial and red soils was quartz sand>red soil>alluvial soil. Further, this study revealed that δ-MnO(2)-enhanced oxidative degradation of pyrene is very pronounced in contaminated soils in situ even at deep soil layers where irradiation by sunlight is very limited.

Sorption of toluene by humic acids derived from lake sediment and mountain soil at different pH.

Contamination of soil and groundwater with BTEX compounds (benzene, toluene, ethylbenzene, and xylene) depends on the sorption behavior of these compounds by soil organic matter (SOM) and humic acids (HAs). In this study sorption of toluene by HAs extracted from lake sediment and mountain soil was investigated. HA suspensions were adjusted to pH 4.00, 6.00, or 8.00 and made to the concentration of 200 mg L(-1). Each HA suspension or solution was subjected to particle size analysis using high performance particle sizer (HPPS). The particle size of HA from lake sediment was around 1000-1200 nm while that from mountain soil was 220-320 nm at suspension pH 4.00. Kinetic studies showed that sorption of toluene by the two HAs followed pseudo-first-order and mainly pseudo-zero-order kinetics. At suspension pH 4.00, the sorption of toluene by the two HAs was best described by Langmuir and Temkin adsorption isotherm models. Further, sorption of toluene by the lake sediment HA was significantly greater than that by mountain soil HA. It was thus suggested that the lake sediment HA with larger particle size may develop beneficially chemical conformation for sorption of toluene and related compounds in soil and associated environments.

Oxidative degradation and associated mineralization of catechol, hydroquinone and resorcinol catalyzed by birnessite.

Abiotic degradation and mineralization of catechol, hydroquinone, and resorcinol catalyzed by birnessite (delta-MnO2) was investigated. Studies were carried out by monitoring changes of pE versus time and pH versus time of the reaction systems during the initial 10 h reaction period and release of CO2 and associated reactions at the end of a 90 h reaction period. The reactions under anoxic condition were compared with aeration condition. The reactions were carried out in suspensions at initial pH of 6.0 under air and N2 atmosphere at room temperature and free of microbial activity. These results indicated that kinetic-related changes of pE versus time and pH versus time were dependent on structural characteristics of phenolic compound and aeration or anoxic condition in the reaction system. The sequence of the mineralization of phenolic compounds catalyzed by delta-MnO2 in presence of air expressed by CO2 release was catechol > hydroquinone > or = resorcinol and the differences were significant. However, under an N2 atmosphere the amounts of CO2 released were drastically reduced with insignificant differences among the three reaction systems. Further, phenolic compound degradations, dissolved and adsorbed Mn, and oxidation state of Mn in delta-MnO2 were also determined to elucidate the catalytic efficacy mediated by both O2 and delta-MnO2 in the reaction systems.

Influence of fertilizers applied to a paddy-upland rotation on characteristics of soil organic carbon and humic acids.

The qualitative and quantitative characteristics of soil organic carbon (SOC) and related humic acids (HAs) extracted from the soils of field plots were investigated after 8 years of annual paddy (Oryza sativa L.) and upland maize (Zea mays L.) rotation with various fertilizations. Seven fertilization treatments were selected: Ck (no inputs); Chem (chemical fertilizer of NPK); Comp (swine compost); Comp + 33% of Chem N rate; Comp + 67% of Chem N rate; GM (legume green manure) + 33% of Chem N rate; and peat + 33% of Chem N rate. Organic and inorganic nitrogen inputs of six treatments were equivalent with respect of nitrogen content, but Comp, GM, and peat treatments were complemented with various amounts of inorganic N. After harvest of the eighth paddy crop, surface soil samples collected from the plots were subjected to soil characterizations and extraction of humic substances, which were used for chemical, spectroscopic (FTIR, 13C NMR, ESR, X-ray diffractometry), delta13C, and 14C dating analyses. The yields of HAs extracted from the seven treatments were significantly different. Treatment containing persistent organic compound such as the peat + 33% N treatment increased the humification process in topsoils and produced higher yield of HA. Spectroscopic analyses revealed that fertilization treatments changed the functional groups, alkyl C, crystalline characteristics, and delta13C ratios of HAs and turnover rate of SOC considerably. The SOC of the peat + 33% N treatment had the highest mean residence time of 3100 years. Various fertilizer treatments are correlated with turnover rate of SOC and related HAs, which are associated with concerned carbon sequestration as well as mitigation of CO2 emission in the soil environment.

Reactions of compost-derived humic substances with lead, copper, cadmium, and zinc.

Thermodynamic stability constants of the formation of complexes from the reactions of humic substances with various metals are usually used as parameters to judge the reactivities of both humic substances and metals. However, in calculating the thermodynamic stability constants, complicated processes for the acquisition of activities of components in reactions are absolutely inevitable. In this study, we investigated the average conditional concentration quotients of the complexes formed from the reaction of metals with humic substances and the relations of these quotients to thermodynamic stability constants. The characterized humic substances including HA (MW>1,000), FA (MW>1,000), and FA (MW<1,000) extracted from a swine compost were prepared to react with Pb, Cu, Cd, and Zn at 25 degrees C and at pH 4.00 and 6.50. Reactions of HA (MW>1,000), FA (MW>1,000), and FA (MW<1,000) with the four metals were carried out at 1:0.1, 1:0.5, 1:1, 1:5, and 1:10 ligand:metal stoichiometry. The concentrations of the free ions of Pb, Cu, Cd, and Zn in the reaction systems of metal-HA suspensions and metal-FA solutions were measured by anodic stripping voltammetry (ASV). The sequence of the average conditional concentration quotients of the formed complexes from the reaction of humic substances with metals was FA(MW<1,000)>FA(MW>1,000)>HA(MW>1,000), showing the relative reactivities of the fractions of swine compost-derived humic substances. The sequence of reacting metals with humic substances was Pb>Cu>Cd>Zn, which is in good agreement with the sequence reported by judging the thermodynamic stability constants. The average conditional concentration quotients of the formed complexes from the reaction of humic substances with metals were thus useful parameters that can be directly related to thermodynamic stability constants and other parameters.