石油污染土壤的原位生物修复技术和多种土壤改良剂应用研究

土壤中的石油污染是一类严重的环境危害.针对石油污染的土壤修复技术有物理法、化学法和生物法.其中原位生物修复法由于简易性和生态可持续等优点成为了具有前景的一个发展方向.土壤改良剂的选取和添加是原位生物修复法中重要的一个部分,对生物修复的改进起到了至关重要的作用.土壤改良剂的种类有无机改良剂、有机改良剂和吸附性改良剂.以N、P、K为主的无机改良剂主要为生物生长提供营养元素;有机改良剂则可提高石油污染物流动性,提供生物碳源;吸附改良剂则通过吸附污染物,减少毒性,提供生物生长依附.通过对不同种类改良剂的分析和讨论,可为生物修复发展提供进一步的理论基础.     

Distribution of PCDDs and PCDFs in Soils Collected from the Denver Front Range - Principal Components Analysis of Diffuse Dioxin Sources (10 pp)

Background, Aims and Scope The Rocky Mountain Arsenal (RMA) is a US Army facility located northeast of Denver, Colorado that has been listed on the National Priorities List (NPL). It is currently being re-mediated under the authority of the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA) and the Superfund Amendments and Reauthorization Act of 1986 (SARA). As part of the remediation activities at RMA, indications were found that a source of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) had existed on the RMA. As a result, investigations were undertaken to assess the possible nature and extent of any potential sources of PCDDs and PCDFs on the RMA site. In addition, other studies were conducted that examined PCDD/PCDF contamination in the Denver area. The goal of these studies was to examine nature and extent of PCDD/PCDF contamination both on the RMA as well as in the surrounding Denver area. The intent of this study was to characterize sources of dioxins (PCDDs) and dibenzofurans (PCDFs) at low environmental concentrations which might have originated from diffuse sources in the Denver Colorado area and in particular, the Rocky Mountain Arsenal (RMA) using Principal Component Analysis (PCA). Methods Over 200 soil samples were collected from the RMA and the Denver area. From the RMA, soil was collected as part of three studies that included a (1) random site-wide sampling of the RMA, (2) soils from the Western Tier Parcel (WTP), and (3) soils from Historic Use areas. Denver area soil samples were collected from five different land use categories: Residential, Agricultural, Open Space, Commercial, and Industrial. PCA was conducted on concentrations of 17 2,3,7,8-substuituted PCDD and PCDF congeners in 220 soil samples collected from the RMA and the Denver Front Range region. Results and Discussion PCA demonstrated the presence of possible minor sources of dioxins on the RMA. Current remediation efforts on RMA will result in the removal of these sources. Samples from the RMA were identified by the presence of a congener profile containing higher chlorinated PCDFs while the Denver Front Range areas were characterized by the presence of higher chlorinated PCDD congeners. The presence of a PCDF signature for the RMA samples does not necessarily indicate a major source of these contaminants on-site. Indeed, the relatively diffuse nature of the sample clusters would argue strongly against the presence of a single large source. Instead, the predominance of the PCDF congeners probably indicates the mixed industrial activities that took place on and near the site. Conclusion PCA results indicate that PCDD/PCDF profiles in soils collected from the RMA differed from those collected from the outlying Denver areas but that a major source of these contaminants was not present. Rather, the diffuse nature of sample clusters from the PCA indicated that the congener profile of RMA samples was most likely a result of the mixed industrial activities that historically have taken place on and near the site. PCA also indicated that many of the 'open area' (peripheral site-wide) RMA soils samples did not differ from Denver are reference congener profiles. This finding was also true for samples collected from the WTP that were essentially indistinguishable from Off-RMA reference samples. In addition, total TEQ concentrations in soils collected from WTP were similar to those measured in soils collected from the Denver Front Range areas indicating that lack of a major source of PCDD/PCDF within the WTP zones of the RMA. Recommendation and Outlook Analytical as well as statistical results of the soil congener data indicate that the WTP soils are indistinguishable from soils collected from non-industrial areas in the Denver area. This finding would support the recent 'de-listing' of the WTP from the other RMA areas and its' transfer to other authorities in the Denver area.     

土壤改良剂联合间套种技术修复重金属污染土壤:田间试验

在田间条件下,验证通过盆栽试验初步筛选出的几种改良剂在玉米和东南景天间套种修复重金属污染土壤的大田实际应用效果.研究结果表明,施用改良剂蘑菇渣肥、云母和沸石能有效降低玉米籽粒和茎叶中的Cd和Pb,玉米籽粒Cd和Pb含量均达到食用标准.蘑菇渣肥显著增加了东南景天对Cd的提取量,腐植酸显著促进了东南景天对Pb的吸收,因此,蘑菇渣和腐植酸可以应用于玉米和东南景天套种系统.施用云母和沸石可以显著提高土壤pH值,降低土壤可交换态Cd/Pb含量,从而降低二种植物对Cd/Pb的吸收;然而,施用蘑菇渣肥和腐植酸却增加土壤可交换/吸附态Cd/Pb含量.植物根系吸收Cd的稳定常数显示该有机吸附态Cd难于被玉米根系吸收.     

莲花山矿区土壤-农作物系统中重金属调控

以广东省莲花山钨矿区耕地为研究点,研究土壤金属含量分布、形态特征及其调控措施。分析耕地土壤中Zn、Cu、Mn、Ni、Pb、Cd、As含量特征,以碱石灰、MnO2、Fe2O3和钙镁磷肥作为改良剂,对矿区污染耕地土壤进行改良,并种植萝卜Raphanus sativus,分析各改良剂对土壤金属形态及其在土壤-农作物界面迁移的影响。研究表明,矿区耕地土壤酸化, Zn、Mn、Pb、Cd和As超过土壤背景值,其中Cd和As污染严重,分别超过背景值的10.2-16.7倍和1.1-1.3倍。碱石灰有效降低耕地土壤pH值,降低土壤Zn、Cu、Mn、Ni、Pb、Cd可溶态含量,减少其在萝卜中积累。萝卜对Pb、Zn、Cd、Cu、Ni累积量与其可溶态含量相关性显著,与总量相关性不显著。Fe2O3、MnO2、钙镁磷肥对耕地土壤Zn、Cu、Ni、Mn、Pb、Cd 生物有效性及其在农作物中累积量无显著影响。矿区耕地土壤分别添加碱石灰、Fe2O3、MnO2,土壤中砷松散结合态含量降低,农作物砷累积量减少。钙镁磷肥对土壤砷形态无显著影响,但能显著降低萝卜中砷的累积量。碱石灰分别与Fe2O3、MnO2、钙镁磷肥相结合改良耕地土壤,比单一改良剂更能有效降低萝卜中砷的累积量。萝卜中砷累积量与松散结合态存在显著正相关性,与Ca-As存在显著负相关性。碱石灰分别和Fe2O3、钙镁磷肥同时加入土壤,能同时地有效降低Zn、Cu、Mn、Ni、Pb、Cd、As的有效性,及其在农作物累积量,因此,这2种改良方式是莲花山矿区土壤金属固定的有效措施。     

砷胁迫下水磷耦合对不同磷效率水稻根表铁膜及其各部位砷含量的影响

为探索缓解水稻砷毒害的农艺措施,以耐低磷水稻99011和低磷敏感水稻99012为材料,通过土培试验,研究水分、磷用量及其交互作用对不同砷浓度酸性土壤中水稻根表铁膜以及植物体内砷分配的影响。结果表明,节水灌溉(干湿交替)明显减少水稻根表铁膜量,降低铁膜、根系、秸秆、颖壳和精米中的砷含量。与30mg·kg-1P2O5相比,180mg·kg-1P2O5能明显减少两个品种水稻的根表铁膜量以及根系和秸秆中的砷含量;对耐低磷品种铁膜砷含量影响不大,但显著降低磷敏感品种铁膜砷含量;在50mg·kg-1砷处理中增加磷用量对水稻颖壳砷含量影响不大,在100mg·kg-1砷处理时能显著降低颖壳砷含量;增加磷用量可明显增加耐低磷品种的精米砷含量,降低磷敏感品种的精米砷含量。水、磷交互效应主要受水分效应的影响。加砷处理后,相同处理下耐低磷品种的根表铁膜量和铁膜中的砷含量显著高于磷敏感品种,而根系、秸秆、颖壳和精米中的砷含量则相反。研究表明,可以通过节水灌溉,并根据砷污染程度和植物磷营养特性确定适当的磷肥用量,从而减少砷在水稻体内的累积,提高食品安全。     

不同碳氮磷源改良剂对铅锌尾矿废弃地植被与土壤性质的影响

开展野外田间试验,在铅锌尾矿废弃地上添加不同碳氮磷源改良剂进行植被重建,从植物生长、营养元素、土壤酶活性、尾矿及植物重金属含量等方面研究其对铅锌尾矿废弃地的改良效果.结果表明:①添加不同碳氮磷源改良剂促进了植物在尾矿上定居和生长,植被盖度从6个月的2. 0%～20. 0%增长到30个月的62. 5%～98. 5%;生物量从6个月的9. 4～115g·m-2增长到30个月的389. 0～2 358. 3 g·m-2.②添加不同碳氮磷源改良剂增加了尾矿营养元素含量(有机碳、水溶性碳、硝态氮和有效磷分别增加了6. 0%～93. 3%、1. 3%～49. 3%、12. 3%～214. 7%和2. 7%～81. 3%)和提高了土壤酶活性(脱氢酶、β-葡萄糖苷酶、脲酶和磷酸酶活性分别提高了0. 3～2. 8、0. 1～1. 4、0. 1～0. 6和0. 1～0. 5倍).③添加不同碳氮磷源改良剂不同程度地降低了尾矿中重金属有效态含量(DTPA-Cd、DTPA-Cu、DTPA-Pb和DTPA-Zn分别下降了2. 5%～40. 2%、1. 4%～25. 6%、1. 4%～15. 2%和0. 4%～24. 9%)和植物体内重金属(Cd、Cu、Pb和Zn分别下降了12. 1%～58. 7%、6. 4%～46. 0%、20. 2%～68. 0%和11. 7%～58. 1%)含量.④Pearson相关性分析表明,植被盖度、生物量与尾矿营养元素和土壤酶活性呈显著正相关,与尾矿重金属有效态含量呈显著负相关;植物地上部分重金属含量与尾矿重金属有效态含量、营养元素和土壤酶活性相关性不明显.综合分析表明,碳氮磷源改良剂是铅锌尾矿废弃地植被恢复良好的改良材料.     

Soil pH and Anion Abundance Affects on Copper Adsorption

Abstract

Copper (Cu) input to agricultural soils results from Cu containing pesticides and/or that in soil amendments, such as manure or sewage sludge. Soil and soil solution properties influence the adsorption and desorption of Cu by the soil, which in turn determines its plant availability and/or phytotoxicities. Effects of different anion enrichment in the equilibrium solution on Cu adsorption by different soils (pH range of 6.2–9.9) were investigated in this study over a range of Cu concentrations. With Cu concentrations in the range of 0–100 mg L^?1 in the equilibration solution, 95–99% of applied Cu was adsorbed by all three soils. The adsorption of Cu was similar regardless of using either 0.01 M CaCl₂ or Ca(NO₃)₂ as the equilibration solution. When the Cu concentration in the equilibration solution was further increased in the range of 500–2000 mg L^?1, the adsorption of Cu decreased from 60 to 24% of applied Cu in two soils with pH 6.2–7.9. In a high pH soil (pH = 9.9), the Cu adsorption decreased from 77 to 34%. Addition of incinerated sewage sludge (ISS) to a Palouse silt loam soil (pH = 6.2) increased the Cu adsorption as compared to that by unamended soil. This was, in part, due to an increase in the soil suspension pH with ISS amendment.     

Soil remediation using in situ immobilisation techniques

The main objective of this study was to investigate the efficiency of different substrates to reduce the extraction of heavy metals concentration in a heavily contaminated soil. Two contaminated soils by Cu and Zn were used to evaluate the effectiveness of eight substrates (calcium carbonate, bentonite, kaolinite, charcoal, manganese oxide, iron oxide, zeolite, phosphate) to reduce metal availability and to study the change of metals speciation in different forms using sequential extraction technique (single step). Sequential extraction technique (single step, 0.11 M acetic acid, HONH₃Cl, H₂O₂+NH₄OAc, Aqua regia) was applied on contaminated soils after and before treatment to evaluate metals speciation. Results indicate that the most effective treatments in decreasing available metal concentrations were calcium carbonate, zeolite and manganese or iron oxide. Metal sequential fractionations indicate that the exchangeable fraction of Cu and Zn in contaminated soils can be transformed into unavailable forms after chemical remediation.     

Response of antioxidants in sunflower (Helianthus annuus L.) grown on different amendments of tannery sludge: its metal accumulation potential

The interaction of metals present in tannery waste and their tolerance in the plants of sunflower (Helianthus annuus L.) was studied in the present paper under field conditions. Effects of 100% tannery sludge and various amendments of tannery sludge (10%, 25%, 35%, 50%, 75%) along with one set of control were studied on the physiological and biochemical parameters of the plant along with their metal accumulation potential after 30, 60 and 90 d after sowing. The plants of H. annuus were found effective in the accumulation of metals (Cr, Fe, Zn and Mn) in roots, shoots and leaves, however, the level of toxic metal, Cr was found below detection limit in the seeds of the plant. The oil was extracted from the seeds of the plant and the level of oil content was increased up to 35% tannery sludge as compared to control followed by decrease at higher tannery sludge ratio. An increase in the chlorophyll, protein, cysteine, non-protein thiol and sugar contents was observed at the lower amendment of tannery sludge at initial exposure periods followed by decrease than their respective controls. Malondialdehyde content in the roots and leaves was increased beyond 50% sludge amendments at all the exposure periods as compared to control. However, proline and ascorbic acid contents of the roots and leaves of the plant increased at all the exposure periods and sludge amendments, compared to their respective controls.     

Response of cowpea and soybean to P and K on terre de barre soils in southern Bénin

Good growth of grain legumes helps food security and protection of the environment but this may require nutrient inputs. A participatory technology development activity explored from 1998 to 2000 the responses of cowpea (Vigna unguiculata) and soybean (Glycine max (L.) Merr.) to inorganic soil amendments (P and K) on terre de barre soils with different levels of degradation in southern Bénin. Adingnigon, on the Abomey plateau, represents a level of severe degradation, while Hayakpa, on the Allada plateau, is still relatively non-degraded. Treatments included: (i) an unamended control, (ii) P fertilizer only, applied in 1998 or 1999, and (iii) P plus K applied in 1999. At Hayakpa, yields without fertilizer were generally moderate to high; responses to P were statistically significant and K application had a significant effect on soybean yield in 2000. At Adingnigon, P application had a large relative effect (30–200%) but a small absolute effect (less than 100 kg/ha) on cowpea and soybean yield. Subsequent K application increased grain yields further (approximately 100 kg/ha) but still not up to the cowpea yield potential. When 13 Mg/ha of organic amendment (chicken manure or cotton seed) were applied to severely degraded plots at Adingnigon with prior grain yields below 200 kg/ha, cowpea yields of more than 500 kg/ha were achieved, approaching their biological potential for the zone. It is clear from this study that (i) P and K inputs are needed for grain legumes even on relatively non-degraded terre de barre soils and (ii) inorganic fertilizer alone will not revive highly degraded soils on the terre de barre plateaus of southern Bénin.