污染土壤的微波辐照技术研究进展

简要介绍了土壤污染的状况,总结了国外学者对重金属和有机物两大类污染土壤所进行的微波修复工作,探讨了修复机理及影响因素,最后展望了微波修复污染土壤的研究重点.     

Biodegradation of trifluralin in Harran soil

Degradation of trifluralin (alpha, alpha, alpha-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) was investigated in soils taken from three different locations at Harran region of Turkey under laboratory conditions. Surface (0-10 cm) soils, which were taken from a pesticide untreated field Gürgelen, Harran-1 and Ikizce regions in the Harran Plain. were incubated in biometer flasks for 350 days at 25 degrees C. Ring-UL-14C-trifluralin was applied at the rate of 2 microg g(-1) with 78.7 kBq radioactivity per 100 g soil flask. Evolved (14)CO2 was monitored in KOH traps throughout the experiment. Periodically, soil sub-samples were removed and extracted by supercritical fluid extraction (SFE). Unextractable soil-bound 14C residues were determined by combustion. During the 350 days incubation period 6.6, 5.4, and 3.3/' of the applied radiocarbon was evolved as (14)CO2 from the Harran-1, Gürgelen, and Ikizce soil, respectively. At the end of 350 days the SFE-extractable and bound 14C-trifluralin residues were 39.0 and 29.2% of the initially applied herbicide in Gürgelen soil. The corresponding values for Harran-1 and Ikizce soils were 36.2, 28.4% and 41.6, 18.5% respectively.     

Combined chemical and biological treatment of oil contaminated soil

Combined chemical (Fenton-like and ozonation) and biological treatment for the remediation of shale oil and transformer oil contaminated soil has been under study. Chemical treatment of shale oil and transformer oil adsorbed in peat resulted in lower contaminants' removal and required higher addition of chemicals than chemical treatment of contaminants in sand matrix. The acidic pH (3.0) conditions favoured Fenton-like oxidation of oil in soil. Nevertheless, it was concluded that remediation of contaminated soil using in situ Fenton-like treatment will be more feasible at natural soil pH. Both investigated chemical processes (Fenton-like and ozonation) allowed improving the subsequent biodegradability of oil. Moderate doses of chemical oxidants (hydrogen peroxide, ozone) should be applied in combination of chemical treatment (both, Fenton-like or ozonation) and biotreatment. For remediation of transformer oil and shale oil contaminated soil Fenton-like pre-treatment followed by biodegradation was found to be the most efficient.     

臭氧氧化降解苯胺黑药模拟废水

苯胺黑药(学名:二苯胺基二硫代磷酸)是一种良好的有色金属硫化矿浮选捕收剂,属于典型的难降解有机污染物。为研究臭氧氧化苯胺黑药的条件和氧化反应的动力学,选用臭氧作为氧化剂,对苯胺黑药浓度和模拟废水的COD进行测定。结果表明,用5 g/h的臭氧氧化20 min后,初始浓度50、75和150 mg/L的苯胺黑药模拟废水的COD去除率分别为56%、59%和76%,苯胺黑药浓度的去除率分别达到100%、99%和88%,反应后废水p H变为强酸性(4)。对应的氧化反应动力学表观一级速率常数k为-0.372 s-1、-0.331 s-1和-0.259 s-1;R2为0.9926、0.9949和0.9903。探讨了臭氧氧化苯胺黑药前后p H变化的机理。     

Photo-Fenton treatment of TNT contaminated soil extract solutions obtained by soil flushing with cyclodextrin

The technical feasibility and performances of coupling flushing abilities of cyclodextrin solutions for 2,4,6-trinitrotoluene (TNT) removal from contaminated soil and the ability of Photo-Fenton treatment for final disposal of soil extract solutions containing high TNT loads have been investigated at laboratory scale. Methylated-beta-cyclodextrin (MCD) has shown better ability than hydroxypropyl-beta-cyclodextrin (HPCD) to complex TNT. The MCD solution increased the aqueous concentration of TNT in soil extract effluents as much as 2.1 times the concentrations obtained during the water flush of the soil. TNT in soil extract solution has been treated by Photo-Fenton. Our results indicate that MCD has a beneficial effect on the degradation rates of TNT. This relative improvement of TNT degradation rate (1.3 time) in presence of high amounts of hydroxyl radical scavengers can be ascribed to the formation of a ternary complex (TNT-cyclodextrin-iron) which can direct hydroxyl radical reaction toward TNT. Complete mineralization of soil extraction solutions was not achieved and TNT degradation pathway has been elucidated in order to ensure that no potential toxic intermediate is left at the end of the treatment time. After successive TNT hydroxylations, oxidative opening of the TNT aromatic ring quickly occurred, leading to the accumulation of short chain carboxylic acids such as oxalic acid and formic acid.     

Effect of manure on glyphosate and trifluralin mineralization in soil

Manure additions to soil may alter soil chemical, physical, and biological characteristics, and thereby change pesticide fate processes in soil. This is the first study to examine the impact of liquid hog manure amendments on glyphosate and trifluralin mineralization in soil. Experiments were conducted in soil microcosms in the laboratory for a total of 332 (glyphosate) and 430 (trifluralin) days. The rate and amount of mineralization of both glyphosate and trifluralin were significantly influenced by the additions of fresh manure to soil in the laboratory and by the history of manure applications in the field. However, the maximum difference in herbicide mineralization between soils that were free of manure application and those amended with manure in the field or in the laboratory was only 6.1% and 7.3% of that initially applied, for trifluralin and glyphosate, respectively. Therefore, we conclude that liquid hog manure application to soil will have no significant effect on the mineralization of glyphosate and trifluralin under field conditions.     

Polychlorinated biphenyls-containing electrical insulating oil contaminated soil treatment with calcium and magnesium peroxides

Calcium and magnesium peroxides were applied for the treatment of soil contaminated by polychlorinated biphenyls-containing electrical insulating oil (Aroclor 1016). The removal of PCB-containing electrical insulating oil was achieved with the addition of either calcium peroxide or magnesium peroxide alone and dependent on dosages of the chemical. A 21-d treatment of 60% watered soil with the moderate addition (chemical/oil weight ratio of 0.005/1) of either calcium peroxide or magnesium peroxide resulted in nearly complete (96 ± 2%) oil removal, unsubstantial increase in soil pH and almost no changes in oxygen consumption and dehydrogenase activity, making it suitable for the soil decontamination.     

Pilot-scale electrokinetic treatment of a Cu contaminated red soil

A pilot-scale experiment for electrokinetic treatment of 700 kg of copper contaminated red soil was conducted using a constant voltage of 80 V. Dynamic removal percentages of Cu from the soil and energy consumption during the treatment were evaluated together with changes of soil pH, electrical conductivity and soil microbial functional diversity before and after the electrokinetic treatment. The results indicate that 76% of Cu was successfully removed from the soil after 140 d of treatment when lactic acid was used as enhancing reagent for adjusting the catholyte pH and dissolving soil Cu by complexation, and the pilot-scale electrokinetic experiment consumed electric energy of 224 kW h t-1 soil. The post-treatment soil pH values decreased about 0.1-1.6 units compared with the initial value (pH 4.8), and soil electrical conductivities in most of soil sections also significantly decreased. Soil microbial functional diversity varied after the electrokinetic treatment, particularly the increase of substrate richness index, which is possibly due to the stimulation of lactic acid that was introduced into the soil column during the experiment.     

A bench-scale investigation of land treatment of soil contaminated with diesel fuel.

A bench-scale investigation (soil pan testing) was conducted with the objective of studying degradation rates of diesel contaminated soil (2500 and 10,000 ppm by weight of total petroleum hydrocarbons (TPH) to dry weight of soil) under different treatment conditions over a 17 week testing period. The greatest degradation of the diesel contaminated soil was obtained with the addition of nutrients (Co = 10,000 ppm of TPH; k = 0.19 week-1). 'k' for soil not amended with nutrients was 0.07 week-1. The control cell (C0 = 2500 ppm TPH), with sodium azide (to suppress degradation) was compared with an experimental cell of 2500 ppm initial concentration of TPH without nutrient amendment. The control cell exhibited a relatively low uniform degradation (k = 0.08 week-1) of TPH over the duration of the experiment with reasonable first-order kinetic regression statistics.     

Ozone oxidation and aerobic biodegradation with spent mushroom compost for detoxification and benzo(a)pyrene removal from contaminated soil

The combination of ozonation and spent mushroom compost (SMC)-mediated aerobic biological treatment was investigated in the removal of benzo(a)pyrene from contaminated soil. The performances of the process alone and combined were evaluated in terms of benzo(a)pyrene removal efficiency, mineralization efficiency (as total organic carbon removal), and soil residual toxicity (phytotoxicity to Lepidium Sativum and toxicity to Vibrio fischeri). In spite of the removal efficiency (35%) obtained by SMC-mediated biological process as a stand-alone treatment, the combined process showed a benzo(a)pyrene concentration reduction higher than 75%; the best removal (82%) was observed after 10 min pre-ozonation treatment. In particular, ozonation improved the biodegradability of the contaminant, as confirmed by the increase of CO(2) production (close to 70% compared to the control), mineralization (greater than 60%) and bacterial density (which increased by two orders of magnitude). Moreover, according to phytotoxicity tests on L. Sativum, the aerobic biological process of pre-ozonated soil decreased toxicity. According to the results achieved in the present study, ozonation pre-treatment showed an high potential to overcome the limitation of bioremediation of recalcitrant compound, but it should be carefully operated in order to maximize PAH removal efficiency as well as to minimize soil residual toxicity which can result from the formation of the oxidation intermediates.     

硫系物对铬污染土壤的还原稳定化处理

采用化学还原技术,添加硫代硫酸钠、硫酸亚铁、连二亚硫酸钠、硫化钠处理某化工厂遗留地的铬污染土壤,考察了4种还原剂处理铬污染土壤的效果。结果表明:在养护时间为30d时,4种还原剂对土壤Cr(Ⅵ)的稳定效率均高于90%,其中采用硫代硫酸钠和硫酸亚铁的稳定效率分别为99.1%和96.8%;硫酸亚铁、硫代硫酸钠、连二亚硫酸钠和硫化钠对土壤Cr(Ⅵ)的还原效率分别为74.2%、64.1%、52.7%、49.2%;连二亚硫酸钠和硫化钠处理后土壤中铬有效态无明显变化,硫酸亚铁和硫代硫酸钠处理后土壤中铬有效态有所下降,占比(质量分数)从原土的27.4%降至14.0%、21.4%,残渣态从原土的23.4%分别增加至39.8%和39.7%,稳定性增强。在相同投加量下,硫酸亚铁是处理铬污染土壤效果最佳的还原剂。     

Effects of trifluralin on soil microbial populations and the nitrogen fixation activities

Effects of trifluralin on soil microbial populations and the nitrogen fixation activity of nitrogen-fixing bacteria Azotobacter chroococcum and Bradyrhizobium japonicum and the decomposition of trifluralin by soil microorganisms were studied. Trifluralin at lower concentrations from 0.5 mg microg(-1) dry soil to lower than 10.0 mg microg(-1) dry soil appeared to stimulate the growth of soil bacteria, actinomycetes, mould, and the pure cultures of Br. japonicum and A. chroococcum. Not only the colony amounts of these two species of nitrogen-fixing bacteria increased, grown on agar medium containing lower concentrations of trifluralin, but also these colonies also enlarged in size and appeared obviously in shorter formation time. However, trifluralin at higher concentrations would inhibit the development of microbial colonies both in amount and size. Trifluralin inhibited the activity of acetylene reduction of A. chroococcum when it was added at the same time of inoculation with A. chroococcum, but it showed a noteworthy stimulation to nitrogen fixation of A.chroococcum when it was put into culture after the cells of the nitrogen-fixing bacterium had grown well. The observation that soil microorganisms could use trifluralin as sole carbon and nitrogen resources for their growth, indicated that microorganisms could decompose trifluralin well.     

有机污染土壤热处理过程中的炭化行为及其影响

热处理技术在国内外均占有较高的市场份额,已成为有机污染场地的主要修复技术。尽管对热处理技术本身的研究和关注较多,包括工艺、参数、能源、效果、成本、应用等方面,但关于有机污染物热处理化学转化中炭化行为研究的报道并不多见。炭化行为可能会改善土壤再利用特性,对热处理工艺参数也可能有一定影响。指出了传统焦化行业中4种炭化反应类型及其机理过程,梳理了石油烃和芳烃化合物等污染土壤热处理过程中的炭化行为,总结了有机污染物炭化行为对土壤再利用特性的影响,并分析了生物质炭化产物对土壤肥力的促进机制。以此为基础,提出了有机污染土壤热处理炭化行为研究的几个重点关注方向。     

Remediation of metal contaminated soil with mineral-amended composts

This study examined the use of two composts derived from green waste and sewage sludge, amended with minerals (clinoptilolite or bentonite), for the remediation of metal-contaminated brownfield sites to transform them into greenspace. Soils contaminated with high or low levels of metals were mixed with the mineral-enhanced composts at different ratios and assessed by leaching tests, biomass production and metal accumulation of ryegrass (Lolium perenne L.). The results showed that the green waste compost reduced the leaching of Cd and Zn up to 48% whereas the composted sewage sludge doubled the leachate concentration of Zn. However, the same soil amended with composted sewage sludge showed an efficient reduction in plant concentrations of Cd, Cu, Pb or Zn by up to 80%. The results suggest that metal immobilisation and bioavailability are governed by the formation of complexes between the metals and organic matter. The amendment with minerals had only limited effects.     

Measurement of trifluralin volatilization in the field: Relation to soil residue and effect of soil incorporation

Volatilization may represent a major dissipation pathway for pesticides applied to soils or crops. A field experiment (September, 2002), consisted in volatilization fluxes measurements during 6 days, covering the periods before and after soil incorporation carried out 24 h after trifluralin spraying on bare soil. Evolution of concentration in soil was measured during 101 days, together with soil physical and meteorological variables. Volatilization fluxes were very high immediately after application (1900 ng m(-2) s(-1)), decreased down to 100 ng m(-2) s(-1) in the following 24 h. Soil incorporation strongly abated trifluralin concentration in the air. 99% of the total volatilization losses recorded over the 6 days following application occurred before incorporation. Volatilization fluxes evidenced a diurnal cycle driven by environmental conditions. Soil trifluralin residues could still be quantified 101 days after application. Our results highlight the caution required when using soil degradation half-life values in the field for volatile compounds.     

The biochemical activity of soil contaminated with fungicides

Excess fungicides can pose a serious threat to the soil environment. Fungicides can lower the microbiological and biochemical activity of soil and lead to yield declines. Soils contaminated with fungicides have to be remediated to maintain the optimal function of soil ecosystems. This study evaluates the effect of neutralizing substances on soil enzymatic activity and the yield of Triticum aestivum L. in soil contaminated with fungicides. Sandy loam (Eutric Cambisols) with pH_KCl 7.0 was contaminated with an aqueous solution of Amistar 250 SC and Falcon 460 EC in the following doses: 0 (soil without fungicide – treated as a control), RD (dose recommended by the manufacturer) and 300?×?RD (dose 300-fold higher than the recommended dose). Soil was supplemented with bentonite and basalt meal at a dose of 10?g kg^?1 DM of soil (dry mass of soil). The fungicide dose recommended by the manufacturer did not induce changes in soil enzymatic activity or the yield of T. aestivum L. Our findings indicate that the tested fungicides can be safely applied to protect crops against fungal pathogens. However, when applied at the dose of 300?×?RD, the tested fungicides strongly inhibited soil enzymatic activity and disrupted the growth and development of spring wheat. Soil supplementation with bentonite and basalt meal improved the yield of T. aestivum L., and bentonite was more effective in reducing fungicide stress. The analyzed substances were not highly effective in restoring biochemical homeostasis in soil.     

Chemical methods and phytoremediation of soil contaminated with heavy metals

The effects of chemical amendments (calcium carbonate (CC), steel sludge (SS) and furnace slag (FS)) on the growth and uptake of cadmium (Cd) by wetland rice, Chinese cabbage and wheat grown in a red soil contaminated with Cd were investigated using a pot experiment. The phytoremediation of heavy metal contaminated soil with vetiver grass was also studied in a field plot experiment. Results showed that treatments with CC, SS and FS decreased Cd uptake by wetland rice, Chinese cabbage and wheat by 23-95% compared with the unamended control. Among the three amendments, FS was the most efficient at suppressing Cd uptake by the plants, probably due to its higher content of available silicon (Si). The concentrations of zinc (Zn), lead (Pb) and Cd in the shoots of vetiver grass were 42-67%, 500-1200% and 120-260% higher in contaminated plots than in control, respectively. Cadmium accumulation by vetiver shoots was 218 g Cd/ha at a soil Cd concentration of 0.33 mg Cd/kg. It is suggested that heavy metal-contaminated soil could be remediated with a combination of chemical treatments and plants.     

对二氯苯污染土壤的植物修复研究

采用种植物的方法.对以对二氯苯(PDCB)为代表的多氯代有机污染物(PCOPs)污染土壤的植物修复进行了研究.以黑麦草、紫花苜蓿和大蒜作为供试植物.在PDCB为1 856μg/kg的污染土壤中种植90 d,研究了不同植物条件下土壤中PDCB的降解情况.结果表明,与空白对照相比.种植物大大提高了土壤中微生物的数量和酶的活性.试验结束后,种植黑麦草、紫花苜蓿和大蒜后,PDCB分别降低82.44%、62.82%和59.59%.种植黑麦草时PDCB降解最快,对PDCB污染土壤修复的效果最好.     

PAHs污染土壤的热修复可行性

以某煤制气厂污染场地中16种US EPA优先控制多环芳烃（Σ16 PAHs）为目标污染物进行了热修复批量实验和可行性实验。热修复批量实验结果表明,当热修复温度为400 ℃、加热时间为8 h时,土壤中的Σ16 PAHs去除率达99.9%。热修复可行性实验选择重污染、中污染和轻污染土壤以400 ℃作为目标温度,恒温72 h进行实验。热修复前后不同程度污染土壤的Σ16 PAHs的总去除率均可达到99.9%,但重污染土壤浓度非常高,部分苯并类物质未达到修复目标值,需进一步延长加热时间或提高加热温度保证达到修复目标值。土壤土工参数影响分析结果表明,热修复后土壤颗粒粒径呈增大趋势,土壤稳定性、抗压强度均增强。此外,土壤中可溶性盐含量增多,盐渍化程度增大。     

污染土壤的淋洗法修复研究进展

污染土壤淋洗技术是修复污染土壤的一种新方法 ,是对污染土壤生物修复的一种补充 ,使污染土壤修复的系统化成为可能。淋洗法主要使用淋洗剂清洗土壤 ,使土壤中污染物随淋洗剂流出 ,然后对淋洗剂及土壤进行后续处理 ,从而达到修复污染土壤的目的。因为淋洗剂的种类和淋洗方式的不同 ,土壤淋洗法可分为许多种类。土壤淋洗法主要受土壤条件、污染物类型、淋洗剂的种类和运行方式等因素影响。综合考虑多方面因素 ,就有潜力设计出经济高效的土壤淋洗系统。土壤淋洗法有很多优点 ,尽管也存在一些问题 ,但其技术上的优势也是其他方法难以取代的 ,所以有良好的应用前景。