Effects of leaching from alkaline red mud on soil biota: modelling the conditions after the Hungarian red mud disaster

A soil column experiment was set up to investigate the effect of red mud from Ajka (Hungary) on a typical soil profile from the affected area. The chemical changes caused by the red mud leachate and the effects of these changes on living organisms were assessed. Ecotoxicological tests were performed with Vibrio fischeri, Sinapis alba and Folsomia candida and the number of aerobic heterotrophic microorganisms was determined. The total, plant-available, exchangeable and water-soluble fractions of Na, Mo, Cu and Cr increased in the soil, mostly owing to their leaching from the red mud layer, but partly to the increase in the pH and DOC concentration. The chemical changes only had significant effects on the test organisms in the 0–30 cm soil layer, except for F. candida, which also had a lower survival rate in the 30–50 cm soil layer. No severe toxic effects were detected in the test organisms; in fact a stimulating effect was revealed for the aerobic heterotrophic cell number and for S. alba germination. However, the red mud itself was toxic, so the ecotoxicological tests justified the removal of red mud from the soil surface after the disaster.     

3种水生植物对锰污染水体修复作用的研究

通过静态水培试验,研究了3种水生植物水葫芦（Eichhornia crassipes（Mart.）Solms）、水浮莲（Pistia stratiotes L.）、水花生（Atlernanthera philoxeroides）在55、155mg L-1锰（Mn）质量浓度下的生物量、Mn质量分数、富集系数、转运系数,以及对2种Mn质量浓度水体的修复作用。结果表明,水浮莲的鲜质量、干质量、相对生长率、Mn质量分数、富集系数随着取样时间的延长而显著增加（P〈0.05）。2种Mn质量浓度下,水葫芦与水浮莲的鲜质量与相对生长率显著高于水花生。植物茎叶的Mn质量分数依次为水浮莲〉水葫芦〉水花生（P〈0.05）,其中155mg L-1Mn处理水浮莲与水葫芦茎叶Mn质量分数均高于10000mg kg-1,分别为12431.05mg kg-1、11238.28mg kg-1。3种植物茎叶、根的富集指数均显著大于1,且茎叶的富集系数依次为水浮莲〉水葫芦〉水花生（P〈0.05）,根富集指数依次为水浮莲≈水葫芦〉水花生（P〈0.05）。在10,21d这2个取样时期,水浮莲的转运系数要高于其它植物,其中在155mg L-1处理下,水浮莲的转运系数要高于1,分别为1.04、1.01。种植3种水生植物后,2种Mn处理水体的Mn质量浓度随着取样时间的延长而降低。水葫芦、水浮莲、水花生收获时,55mg L-1Mn处理的水体Mn质量浓度分别降低了31.84%、31.44%、18.47%;155mg L-1Mn处理则降低了12.02%、18.53%、7.57%。可见,水浮莲符合超积累植物对Mn质量分数、富集系数、转运系数的要求,其在Mn污染水体修复方面有很好的应用前景。     

Gypsum addition to soils contaminated by red mud: implications for aluminium, arsenic, molybdenum and vanadium solubility

Red mud is highly alkaline (pH 13), saline and can contain elevated concentrations of several potentially toxic elements (e.g. Al, As, Mo and V). Release of up to 1 million m³ of bauxite residue (red mud) suspension from the Ajka repository, western Hungary, caused large-scale contamination of downstream rivers and floodplains. There is now concern about the potential leaching of toxic metal(loid)s from the red mud as some have enhanced solubility at high pH. This study investigated the impact of red mud addition to three different Hungarian soils with respect to trace element solubility and soil geochemistry. The effectiveness of gypsum amendment for the rehabilitation of red mud-contaminated soils was also examined. Red mud addition to soils caused a pH increase, proportional to red mud addition, of up to 4 pH units (e.g. pH 7 → 11). Increasing red mud addition also led to significant increases in salinity, dissolved organic carbon and aqueous trace element concentrations. However, the response was highly soil specific and one of the soils tested buffered pH to around pH 8.5 even with the highest red mud loading tested (33 % w/w); experiments using this soil also had much lower aqueous Al, As and V concentrations. Gypsum addition to soil/red mud mixtures, even at relatively low concentrations (1 % w/w), was sufficient to buffer experimental pH to 7.5–8.5. This effect was attributed to the reaction of Ca²⁺ supplied by the gypsum with OH^? and carbonate from the red mud to precipitate calcite. The lowered pH enhanced trace element sorption and largely inhibited the release of Al, As and V. Mo concentrations, however, were largely unaffected by gypsum induced pH buffering due to the greater solubility of Mo (as molybdate) at circumneutral pH. Gypsum addition also leads to significantly higher porewater salinities, and column experiments demonstrated that this increase in total dissolved solids persisted even after 25 pore volume replacements. Gypsum addition could therefore provide a cheaper alternative to recovery (dig and dump) for the treatment of red mud-affected soils. The observed inhibition of trace metal release within red mud-affected soils was relatively insensitive to either the percentage of red mud or gypsum present, making the treatment easy to apply. However, there is risk that over-application of gypsum could lead to detrimental long-term increases in soil salinity.     

有机氯农药六六六污染土壤的植物修复研究

我国20世纪六七十年代大量施用的有机氯农药,由于其性质极其稳定,在土壤至今仍有残留。植物修复有机农药污染土壤并不多见,但具有广阔的应用前景。此项研究对提高土壤环境质量、保证农产品的安全、实现农业可持续发展等有着重要的理论和现实意义。文章以多花黑麦草(Lolium multiforum Lan.)、紫花苜蓿(Medicago sativa L.)和籽粒苋(Amaranthus hypochondriacus L.)作为供试植物,在有机氯农药六六六(HCH)质量分数为1.09 mg.kg-1的污染土壤中种植3个月,研究了种植不同植物条件下土壤中HCH的消解情况。研究结果表明,与对照相比,种植植物大大提高了土壤中微生物数量和酶的活性,并且微生物的数量和酶的活性与土壤中HCH的消解密切相关。试验结束后,不同处理中HCH及其4种异构体的总含量降低幅度为43.87%~65.79%,其中种植紫花苜蓿和多花黑麦草的处理中HCH消解较快,对HCH污染土壤修复的效果较好。可见,植物修复技术是一种可行的环境友好的修复六六六污染土壤的技术。     

Cerium-tungsten oxides supported on activated red mud for the selective catalytic reduction of NOx

Activated red mud(RM) has been proved to be a promising base material for the selective catalysis reduction(SCR) of NO_x.The inherent low reducibility and acidity limited its low-temperature activity.In this work,molybdenum oxide,tungsten oxide,and cerium oxide were used to reconfigure the redox sites and acid sites of red mud based catalyst.When activated red mud was reconfigured by cerium-tungsten oxide(CeW@RM),the NO_x conversion kept above 90% at 219-480℃.The existence of...     

Assessing human bioaccessibility of trace contaminants in size-fractionated red mud,derived precipitates and geopolymeric blocks

The objective of this study was to provide insight into human exposure to trace contaminants bearing red mud, derived precipitates and geopolymeric blocks due to inhalation contact and/or hand-to-mouth ingestion. The in vitro bioaccessibility behavior of trace contaminants was investigated with the PBET (physiologically based extraction test), ALF (artificial lysosomal fluid) and MGS (modified Gamble’ solution) methods. The results showed that total contents of trace contaminants and operation parameters, such as pH and chelating properties of simulated gastrointestinal phases (PBET), played a joint role in controlling the bioaccessibility efficacy for size-fractionated red mud particles. As for airborne particles (<38 μm size fractions), trace contaminants concentrations extracted by MGS was significantly higher than those by ALF. Additionally, higher bioaccessibility (PBET) values of Cu, Pb, Zn, As, V and U were obtained from red mud derived precipitates compared with those of red mud itself. Even though short-term and long-term leaching values of trace contaminants were relatively lower in the prepared geopolymeric blocks, the health risk could be significantly higher due to the more pronounced bioaccessibility characteristics.

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Nutrients Can Enhance Phytoremediation of Copper-Polluted Soil by Indian Mustard

An orthogonally designed experiment was conducted to study the single and combined effects of N, P and K on phytoremediation of Cu-polluted soil by Indian mustard. Addition of fertilizer N and P significantly increased Indian mustard shoot yield. Two high treatments combined with N resulted in the highest yields, followed by low-P combined with N. In contrast, high P with no N gave no yield increase and K had no effect on yield of Indian mustard. Nitrogen and P increased the amount of chlorophyll in the leaves, indicating that the yield increases were due to enhanced photosynthesis. Nitrogen application had no effect on plant Cu concentrations but addition of P slightly decreased plant Cu concentrations, likely a dilution effect resulting from the increase in yield. Among the treatments, N and P applied at 100 and 200 mg kg^–1 respectively with no K application resulted in the highest Cu uptake. Thus, a combination of low N and high P produced a yield increase in Indian mustard that was more than adequate to compensate for a slight decrease in Cu concentration, resulting in the highest Cu removal from the contaminated soil.     

Effects of rape straw and red mud on extractability and bioavailability of cadmium in a calcareous soil

Screening of cost-effective soil amendments is important to develop “in situ” remediation techniques for cadmium (Cd) contaminated soils. In this study, different soil amendments, including red mud, a by-product of the alumina industry, and acid-treated, nano-treated by nano-particle milling, nano and acid-treated red muds, zeolite, corn straw, and rape straw, were evaluated to immobilize Cd in two added levels (2 and 5 mg Cd·kg^-1 soil) in a calcareous soil by single and sequential extractions and by cucumber (Cucumis sativus L.) pot experiments. Results indicated that cruciferous rape straw significantly decreased the concentrations of water soluble, extractable Cd in soils, and Cd in cucumber plants, and it was more effective than gramineous corn straw. Also, red mud generally decreased the extractability and bioavailability of Cd added to calcareous soils more effectively than zeolite. Furthermore, the efficiency of red mud could be increased by the treatment of nano-particle milling due to the increase in specific surface area of red mud. It is potential to use rape straw and red mud as soil amendments to develop a cost-effective and efficient “in situ” remediation technology for Cd mildly contaminated calcareous soils.     

赤泥基零价铁类芬顿降解罗丹明B和磺胺嘧啶的催化性能

为了有效去除废水中的有机污染物和实现赤泥(RM)的再利用,利用废弃活性炭(WAC)作为碳源,通过还原焙烧-磁选二步法制备了赤泥基零价铁(ZVI/RM)材料作为类芬顿催化剂催化氧化废水中常见的有机污染物罗丹明B (RhB)和磺胺嘧啶(SD).材料表征结果表明,零价铁均匀分布在材料上,且材料具有明显的介孔结构.当初始pH为...     

Precise regulation of acid pretreatment for red mud SCR catalyst: Targeting on optimizing the acidity and reducibility

• The optimum SCR activity was realized by tuning the acid pretreatment. • Optimized catalysts showed NO_x conversion above 90%. • The NH₃ and NO adsorption capacity of Al-O₃-Fe is stronger than Fe-O₃-Fe. • The formation of almandine consumes Fe³⁺ and Al³⁺ and weakens their interaction. Red mud (RM), as an alkaline waste, was recently proved to be a promising substitute for the SCR catalyst. Dealkalization could improve the acidity and reducibility of red mud, which were critical for SCR reaction. However, the dealkalization effect depended on the reaction between acid solution and red mud. In this study, we realized the directional control of the chemical state of active sites through tuning the acid pretreatment (dealkalization) process. The pretreatment endpoint was controlled at pH values of 3–5 with diluted nitric acid. When the pH values of red mud were 3 and 5 (CRM-3 and CRM-5), activated catalysts showed NO_x conversion above 90% at 275°C–475°C. The high initial reaction rate, Ce³⁺/(Ce³⁺ + Ce⁴⁺) ratio, and surface acidity accounted for the excellent SCR performance of CRM-5 catalyst. Meanwhile, more Fe³⁺ on the CRM-3 surface improved the NH₃ adsorption. There was a strong interaction between Al and Fe in both CRM-5 and CRM-3 catalysts. DFT results showed that the adsorption capacity of the Al-O₃-Fe for NH₃ and NO is stronger than that of Fe-O₃-Fe, which enhanced the NO_x conversion of the catalyst. However, the almandine was formed in CRM-4, consumed part of Fe³⁺ and Al³⁺, and the interaction between Al and Fe was weakened. Also, deposited almandine on the catalyst surface covered the active sites, thus leading to lower NH₃-SCR activity.     

Stabilization of Cd-, Pb-, Cu- and Zn-contaminated calcareous agricultural soil using red mud: a field experiment

Red mud (RM) was used to remediate heavy metal-contaminated soils. Experiments with two different dosages of RM added to soils were carried out in this study. It was found that soil pH increased 0.3 and 0.5 unit with the dosage of 3 and 5% (wt%), respectively. At the dosage of 5%, the highest stabilization efficiencies for Cd, Pb, Cu and Zn reached 67.95, 64.21, 43.73 and 63.73%, respectively. The addition of RM obviously transferred Cd from the exchangeable fraction to the residual fraction. Meanwhile, in comparison with the control (no RM added), it reduced 24.38, 49.20, 19.42 and 8.89% of Cd, Pb, Cu and Zn in wheat grains at the RM addition dosage of 5%, respectively. At the same time, the yield of wheat grains increased 17.81 and 24.66% at the RM addition dosage of 3 and 5%, respectively. Finally, the addition of RM did not change the soil bacterial community. These results indicate that RM has a great potential in stabilizing heavy metals in calcareous agricultural soils.

     

Effect of red mud addition on the fractionation and bio-accessibility of Pb,Zn and As in combined contaminated soil

Using soil incubation experiments, the effect of red mud addition on the fractionation and bioaccessibility of Pb, Zn and As in combined contaminated soil was studied. The results showed that red mud addition could significantly decrease the concentration of HOAc-extractable Pb and Zn in soil. Compared with the control, 5% red mud addition could significantly reduce the concentrations of HOAc-extractable Pb and Zn in soil after 1, 2 and 3 months of incubation [62.5, 65.3 and 73.5% decrease (Pb), 56.7, 65.8 and 67.4% decrease (Zn)]. Whereas adding red mud could remarkably increase the concentrations of specific absorbed As and residual As in soil. The result of a simple bioavailability extraction test (SBET) indicated that all treatments with red mud addition markedly reduced the concentration of bioaccessible Zn but increased the concentration of bioaccessible As in soil, while having little effect on the concentration of bioaccessible Pb in soil. After 3 months incubation, all treatments including 1, 2 and 5% red mud addition reduced the concentration of bioaccessible Zn by 53.1–56.7% compared with the control, but increased the concentration of bioaccessible As by 1.81–6.25 times. The results suggested that red mud is an additive with potential for the remediation soil contaminated soil by combinations of heavy metals, although it should be added based on the different heavy metals in the soil. Combined use of red mud and hyperaccumulators to remediate heavy metal contaminated soil needs further study.     

Phytoremediation of landfill leachate using Pennisetum clandestinum

Landfills are still the most widely used solid waste disposal method used across the world. Leachate generated from landfill areas exerts environmental risks mostly on surface and groundwater, with its high pollutant content, most notably metals, which cause an unbearable lower water quality. During dumping or after the capacity of the landfill has been reached, a decontamination and remediation program should be taken for the area. This study was conducted to assess the capacity and efficiency of Pennisetum clandestinum, a prostrate perennial plant, to accumulate chromium (Cr), copper (Cu), iron (Fe), nickel (Ni), zinc (Zn) and lead (Pb). Leachate, taken from the Sofulu Landfill Site, was given to Pennisetum clandestinum for 180 days, in 3 dilution sets as 1/1, 1/2 and 1/4, in batch configuration. An additional control set was also installed for comparison. Results showed that, even though the metal content of soil had risen, plants accumulated 2 to 8.5 times higher concentrations than the control set. It is important to see, the plant showed almost no stress symptoms even if the set was fed by pure leachate. Pennisetum clandestinum was observed to accumulate metals mostly in the upper bodies, excluding Fe and Cu. 76% of accumulated Cr, 85% of Ni, 66% of Zn and 100% of Pb was observed to accumulate in above-ground parts, where only 20% of Cu and 4% of Fe was accumulated. Due to the high pollution tolerance of Pennisetum clandestinum, makes this plant suitable for decontamination and remediation of landfill sites.     

多环芳烃污染土壤的微生物-紫花苜蓿联合修复效应

微生物-植物联合修复技术作为一种低耗高效的新型修复手段已经被广泛应用于有机污染土壤的修复领域并取得了较好的效果,新型生物资源的应用将推动该方法的进一步发展。本研究采用温室盆栽实验,以里氏木霉（Trichodermaressei FS10-C）、根瘤菌（Rhizobium meliloti）和紫花苜蓿（Medicago sativa L.）作为供试生物,设置添加灭活菌剂-无紫花苜蓿（CK）、添加灭活菌剂-种植紫花苜蓿（A）、接种木霉菌剂-种植紫花苜蓿（TA）、接种木霉菌根瘤菌复合菌剂-种植紫花苜蓿（TRA）4种处理,探究微生物-植物联合修复对多环芳烃（PAHs）污染土壤的生物修复效果及其微生态效应。结果表明,经过60 d的培养,微生物不仅促进了紫花苜蓿的生长,而且在紫花苜蓿的协同作用下进一步提高了土壤中PAHs降解率。TA处理中紫花苜蓿生物量增加了5.88%,而TRA处理进一步促进了紫花苜蓿的生长,其生物量增加了11.15%;A、TA和TRA处理下土壤中PAHs的降解率分别为17.02%、25.62%、32.93%,显著（p〈0.05）高于处理CK（5.67%）。此外,接种菌剂处理（TA、TRA）对土壤中高分子量PAHs具有更好的降解效果,A处理土壤中4-、5（＋6）环PAHs的降解率分别为18.13%、24.74%,TA处理为21.41%、28.34%,而TRA处理则为21.29%、30.11%。同时,紫花苜蓿能够通过其根际效应显著促进土壤微生物活性,相较于CK处理,A、TA、TRA处理土壤脱氢酶活性分别提高了33.20%、34.58%、32.65%,A、TA、TRA处理AWCD值和微生物群落多样性指数均显著（p〈0.05）高于CK。通过木霉、根瘤菌与紫花苜蓿联合作用不仅可以有效地降解土壤中的PAHs,而且能够恢复土壤微生物生态功能多样性和稳定性。因此,该方法是一种极具潜力的生物修复手段,具有广阔的市场应用前景。     

利用美洲商陆修复锰尾渣污染土壤对后茬植物的影响

采用盆栽法研究用锰超富集植物美洲商陆(Phytolacca americana)修复锰尾渣污染土壤对后茬植物大豆(Glycine max)和绿豆(Phaseolus radiatus)的影响.经美洲商陆修复锰尾渣污染土壤后,后茬植物大豆和绿豆的镉、铅、锌和锰含量降低,污染土壤的毒性减弱,有利于这2种植物生长.经美洲商陆修复2～3 a,可显著减弱污染土壤对大豆的毒性.由此可见,在经美洲商陆修复的污染土壤上栽培大豆,可以增加含氮量,促进其他植物生长,从而维持锰尾渣污染区植被持续发展.     

Insight into the promotion mechanism of activated carbon on the monolithic honeycomb red mud catalyst for selective catalytic reduction of NOx

• Activated carbon was proposed to be an efficient accelerant for molded red mud catalyst. • The surface acidity and reducibility were highly improved, as well as the pore structure. • The enrichment of the surface Fe²⁺ and the adsorbed oxygen account for the improvement. Our previous study proved that the acid-pretreatment process could efficiently activate red mud (RM) for the selective catalytic reduction (SCR) of NO_x. However, in terms of the molding process, which is the key step determining whether it can be applied in large-scale industrial, the surface acidity and reducibility of catalyst always decreased dramatically, and part of surface area and pore structure were lost. In this study, we prepared monolithic honeycomb red mud (MHRM) catalysts with activated carbon (AC) as an accelerant and investigated the effect of AC on the MHRM. The results showed that the MHRM with 3 wt.% of AC (MHRM-AC3) exhibited the best SCR performance, and kept more than 80% NO_x conversion in the range of 325°C–400°C. Compared with the MHRM, MHRM-AC1, and HMRM-AC5, the MHRM-AC3 has more mesoporous and macroporous structures, which can provide more adsorption active sites. The AC significantly improved NH₃ adsorption and surface reducibility, which was mainly due to the increase of the surface acid sites (especially the Brönsted acid sites), the concentration of Fe(II), and the surface adsorbed oxygen. The presence of more Fe(II) enriched the surface oxygen vacancies, as well as the surface adsorbed oxygen, due to the charge imbalance and unsaturated chemical bond. And surface adsorbed oxygen exhibited more active than lattice oxygen owing to its higher mobility, which was conducive to NO_x reduction in the SCR reaction.     

丛枝菌根真菌对紫花苜蓿与黑麦草修复多环芳烃污染土壤的影响

通过温室盆栽试验,研究接种土著与外源丛枝菌根(AM)真菌对紫花苜蓿与黑麦草修复多环芳烃(PAHs)污染土壤的影响.结果表明,接种外源AM真菌--苏格兰球囊霉(Glomus caledonium)36号能够显著提高紫花苜蓿和黑麦草的AM真菌侵染率并促进植物生长,而接种土著菌剂或土著菌剂与36号菌剂双接种对AM真菌侵染和植物生长无促进作用,甚至降低了黑麦草苗期的AM真菌侵染率.种植紫花苜蓿和黑麦草促进了土壤中PAHs的降解,这2种植物接种36号菌剂的处理60天时土壤PAHs降解率分别达42.3%和41.1%,说明36号菌剂可以显著提高植物修复效率,而接种土著菌剂对修复作用无显著影响,土著菌剂与36号菌剂双接种对紫花苜蓿的修复效果也无显著影响,但60天时显著提高黑麦草的修复效率.土壤中PAHs降解率与植物根系的AM真菌侵染率呈显著正相关关系(P<0.05),表明AM真菌侵染可以提高紫花苜蓿与黑麦草对PAHs污染土壤的修复效率.     

Decarboxylation of environmental L-leucine by marine red algae

The uptake and metabolism of ¹⁴C-L-leucine by Cystoclonium purpureum (Huds) Batt. (Rhodophyllidaceae) at concentrations of 0.5–50 μM were studied. Leucine was taken up from seawater at rates of 10–160 nmol·g^-1 fresh weight·h^-1. At low leucine levels ( 5 μM) the amino acid was preferably incorporated into cellular protein; amine formation was less than 5%. However at leucine concentrations of 50 μM, more than 30% of the total leucine taken up was decarboxylated to 3-methylbutylamine. This effect is expressed even more in Dumontia increassata (O. F. Müll) Lamour. (Dumontiaceae). In both species some of the amine occurred as a non-volatile derivative (bound amine) from which free amine could quantitatively be released by acid hydrolysis. Leucine and amine uptake were inhibited by CCCP. However, from cells preloaded with both leucine and amine, only free amine is released in the presence of CCCP. The results indicate that decarboxylase activity will be switched on at increased levels of amino acids in seawater which may be expected frequently in habitats of littoral algae (tidal zone). A possible function of amine formation and release within the scope of chemical defence of benthic algae is discussed.     

湿地碳汇功能探讨:以泥炭地和芦苇湿地为例

大量研究表明湿地是地球表层系统中的重要碳汇,对于吸收大气中的温室气体,减缓全球气候变暖有重要作用.由于近几十年来全球气候变暖和人类活动的影响,湿地碳汇功能不断减弱.文章以泥炭地和芦苇Phragmites australis湿地为例来分析湿地的碳汇功能发现:农业排水、土地利用方式的改变、大气中CO2体积分数升高、全球气候变化等人为和自然因素影响了泥炭地的碳汇功能,泥炭地的碳蓄积能力下降,逐渐由"碳汇"转变为"碳源";尽管芦苇湿地是CH4的重要来源,但其对CO2具有较强的碳汇作用,综合来看芦苇湿地的仍是温室气体的净汇;人工芦苇湿地污水净化系统的温室气体排放量高于天然芦苇湿地.分析表明,研究泥炭地和芦苇湿地在全球气候变化下的响应及反馈机制,确定合理的湿地开发模式将是未来湿地碳汇研究的主要方向.