Arsenic removal from groundwater by a newly developed adsorbent.

A novel adsorbent, which had been developed for phosphate adsorption, was adopted for arsenic removal from groundwater. Adsorption isotherm, pH dependence of the isotherm and adsorption rate were studied by batch method. Furthermore, by using a granular adsorbent of 1.8 mm diameter which is commercially available, lab-scale experiments of continuous adsorption treatment of actual groundwater containing arsenic at 50 mg m(-3) were conducted to examine the performance of the adsorbent. A large amount of arsenic, i.e., 10 g As kg(-1), was adsorbed at pH 7.0 and 10 mg As m(-3) in equilibrium concentration. It was only a 5% higher amount compared to conventional activated alumina. However, twice the bed volume, i.e., total volume of effluent divided by empty column volume, was achieved till breakthrough by using this novel adsorbent. This may be because the pH decrease, which enlarges apparent adsorption capacity of the adsorbent, is caused by a self-pH decrease function of the adsorbent. The self-pH decrease function must be delivered by dissociation of Al (III) aquoion. The proton release was clearly observed in batch experiments.     

Application of iron-coated sand and manganese-coated sand on the treatment of both As(III) and As(V).

In this study, manganese-coated sand (MCS) and iron-coated sand (ICS) were applied in the oxidation of As(III) and adsorption of As(V), respectively. ICS and MCS were prepared by mixing FeCl3 and Mn(NO3)2, respectively, with Joomoonjin sand at 150 degrees C. In the batch adsorption isotherms, adsorption of As(III) and As(V) onto ICS followed a Langmuir type. ICS showed a greater capacity in the removal of As(V) than As(III) and also in the removal of As(V) compared with MCS. Three different configurations of ICS and MCS were used to investigate the oxidation of As(III) and adsorption of As(V) in a column. In the homogenised system, arsenic breakthrough was approximately two-times delayed compared with the separately packed systems. After breakthrough of arsenic, concentration of As(III) in the effluents was below 40 ppb for the entire reaction period in all configurations, and most arsenic was identified as As(V) owing to near complete conversion of As(III) to As(V) by MCS. The catalytic activity of MCS on the oxidation of As(III) was maintained up to 700 pore volumes, which corresponds to the treatment of at least 300 mg As(III) based on the 1 kg MCS. Compared with the homogenised column, the released Mn(II) concentration from two-staged and four-staged columns was great for the entire reaction period. In the case where the same amount of ICS and MCS was packed in a filtration system, the homogenised column was identified as a better configuration compared with the two-staged and four-staged columns when considering the arsenic breakthrough time as well as the released concentration of Fe(III) and Mn(II).     

鲁北平原养鸡场周边包气带与地下水砷化合物分布规律

洛克沙胂(3-硝基-4-羟基苯胂酸)被广泛用作饲料添加剂,但大部分以原体形式随粪便排出,进入环境的洛克沙胂在微生物和光照作用下最终转化为毒性较大的As(V)和As(III)等,并在雨水或农灌的淋滤冲积下污染周边土壤、地表水和地下水。以鲁北平原某养鸡场为研究区,对鸡粪、饲料、周边表层土壤、鸡粪堆积和背景包气带垂向剖面以及地下水进行洛克沙胂及其代谢物的检测,结果饲料中洛克沙胂浓度为34mg/kg,鸡粪中HAPA(3-氨基-4-羟基苯胂酸)浓度为11 mg/kg,距离鸡场越近的表层土壤砷含量越高。三个包气带垂向剖面均以As(V)为主,As(III)含量较小。鸡粪堆积处垂向剖面上HAPA、As(V)和As(III)在土壤表层含量最高,浓度随深度增加而呈下降趋势,同时受到土壤岩性的影响,砷化合物主要的吸附层位为0~30cm与200cm以下;背景包气带垂向剖面上各砷化合物含量均明显低于鸡粪堆积处包气带垂向剖面的砷化合物含量;在鸡场内旧井中检测到浓度为165μg/kg的As(V)。结果证实鸡粪堆积导致土壤包气带、周边土壤和地下水砷含量增加,且这种污染很难消除。     

Arsenic removal by iron and manganese coated sand.

In this study, as a promising technique for the treatment of both As(III) and As(V) at the same time in a single reactor, a column reactor containing both manganese-coated sand (MCS) and iron-coated sand (ICS), at different configuration of MCS and ICS, was used to treat wastewater contaminated with As(III). Prior to column experiments, batch experiments for the adsorption of As(V) by ICS were performed with variation of solution pH, ionic strength and types of background ions to investigate the effect of these parameters on the As(V) adsorption behaviour. As(V) adsorption onto ICS was quite similar with the variation of ionic strength by using NaNO3 as a background ion as well as in the presence of different types of background ions except phosphate. The adsorption curves shifted to the lower pH region with the increase of the initial arsenic concentration due to the finite number of adsorption sites on the ICS. For model prediction on the adsorption of As(V) onto ICS, the MINEQL program employing an inner-sphere complexation and a diffuse layer model was used. Model predictions generally agreed well with experimental results. From the column test, column system packed with equal ratio of MCS and ICS was identified as the best system due to a promising oxidation efficiency of As(III) to As(V) by MCS and adsorption of As(V) by both MCS and ICS.     

Behaviour of arsenic species in batch activated sludge process: biotransformation and removal.

The behaviour of As(III), As(V), MMA(v) and DMA(v) in batch activated sludge process were investigated. Experiments were carried out by using aerobic and anoxic reactors with an initial As concentration of 100 microjg I(-1). Under aerobic condition, As(III) was oxidized to As(V) within 9 hours, some part of MMA(v) was methylated to DMA(v) and some other part was demethylated to As(III), which in turn was immediately oxidized to As(V). Under anoxic condition, As(V) was reduced to As(III) within the same time-course. No significant transformation occurred during experiments conducted with DMA(v). It was found that all reactions were biologically mediated. The overall As removal was low (< 20%) during the experiments. Although a relationship seems to exist between the sludge concentration and As removal, it is concluded, under the conditions of our study, that the activated sludge process cannot remove arsenicals efficiently. However, it can control their transformations well. Thus, if associated with an appropriate technology, the activated sludge can be used for As pre-oxidation to treat As contaminated wastewaters. Finally, care must be taken on possible presence of MMA(v) in the influent of any wastewater treatment plant as it can be easily oxidized by the activated sludge.     

Influence of groundwater composition on subsurface iron and arsenic removal

Subsurface arsenic and iron removal (SAR/SIR) is a novel technology to remove arsenic, iron and other groundwater components by using the subsoil. This research project investigated the influence of the groundwater composition on subsurface treatment. In anoxic sand column experiments, with synthetic groundwater and virgin sand, it was found that several dissolved substances in groundwater compete for adsorption sites with arsenic and iron. The presence of 0.01 mmol L(-1) phosphate, 0.2 mmol L(-1) silicate, and 1 mmol L(-1) nitrate greatly reduced the efficiency of SAR, illustrating the vulnerability of this technology in diverse geochemical settings. SIR was not as sensitive to other inorganic groundwater compounds, though iron retardation was limited by 1.2 mmol L(-1) calcium and 0.06 mmol L(-1) manganese.     

生物固锰除锰技术的微生物学研究

Mn~(2+)氧化细菌的微生物学研究是与除锰工艺直接相关的一个领域。已经发现许多细菌具有锰氧化能力。目前的研究工作基本局限在细菌形态观察和细胞悬液、细胞破碎液的活力动力学测量。因此研究了分离得到的Mn~(2+)氧化细菌,包括其形态、生理研究。同时对其氧化活性进行了测量。可以确认,滤池中存在着大量的Mn~(2+)氧化细菌,细菌参与了除锰。     

荷兰地下水中的砷对饮用水供给的影响

介绍了荷兰饮用水的供给状况,地下水中砷的分布,饮用水中的砷,以及8个典型水文系统中砷的形成过程、水化学特征,分析了荷兰地下水中砷的活动过程,主要包括:吸附和阴离子交换、黄铁矿的氧化反应和氧(氢氧)化铁的还原性溶解以及砷酸盐被还原成亚砷酸盐,并针对不同的情况提出了相应的治理措施。     

改性陶土颗粒吸附砷的实验研究

以赤玉土为骨料烧制陶土材料,经FeCl3溶液浸渍及热处理改性后制备成新型的改性陶土颗粒吸附剂,对其表面特征及除砷性能进行初步研究:BET测定得出该吸附剂比表面积为36.493m2/g,孔容量为0.070mL/g;SEM EDX显示吸附剂表面有大量铁、氧元素分布;对比该吸附剂和HCl溶液改性吸附剂表面的微观数码照片及3D影像图,表明该吸附剂表面存在大量铁氧化物;该吸附剂在中性pH范围内有良好吸附除砷能力,共存的氟离子、磷酸根离子对除砷效果有不同程度的竞争影响,碳酸根离子对除砷效果无显著影响;Freundlich等温线方程能较好地拟合As(V)的吸附过程(R2=0.9927),吸附平衡时的饱和吸附容量可达43.491mg/g。低成本高效的改性陶土颗粒应用于实际的砷吸附处理,具有较好的应用前景。     

贵州省都柳江砷污染事件的应急供水技术与实施要点

2007年12月底发生的贵州都柳江砷污染事件,造成下游三都县县城水厂被迫停水。清华大学张晓健教授及其课题组于2008年1月2日前往现场协助当地开展应急供水工作。应急处理采用了预氯化铁盐混凝法除砷净水工艺,先采用预氯化把水中可能存在的三价砷(亚砷酸)氧化成五价砷(砷酸氢根),再采用铁盐混凝剂混凝,用氢氧化铁絮体络合吸附砷酸根或是形成难溶的砷酸铁沉淀物,从而通过混凝沉淀过滤的净水过程进行除砷处理。经现场试验、设备改造、生产性运行调试和水质监测,应急除砷处理取得成功,出水达到《生活饮用水卫生标准》的水质要求,三都县县城水厂从1月6日15:00恢复正常供水,成为应对突发性砷污染的城市应急供水国内首次成功案例。     

吸附法去除饮用水中砷的研究进展

介绍砷的分布以及饮用水中砷超标的危害,综述当前国内外用不同吸附方法去除饮用水中砷的研究进展,分析其吸附性能和特点。结果表明,在归纳的6种吸附除砷方法中,复合材料与改性材料除砷效率高,处理费用低,目前最具有市场应用前景;活性材料的吸附效果受pH值控制;含铁矿物材料在除砷过程中易导致二次污染;纳米材料除砷效率最高,应是今后的主要发展方向。     

Advanced treatment of benzothiazole contaminated waters: comparison of O3, AC, and O3/AC processes.

Benzothiazole (BT) is a toxic and poorly biodegradable contaminant, usually found in wastewater from rubber related applications. This compound could be effectively eliminated using advanced treatment processes. This paper compares experimental results on detoxification systems based on ozone oxidation, activated carbon adsorption, and simultaneous adsorption-oxidation using ozone in the presence of activated carbon. The effect of pH (2-11), and the presence of radical scavengers (tert-butyl alcohol and sodium carbonate) on process rates and removal efficiencies are assessed at laboratory scale. The experimental system consisted of a 1 L differential circular flow reactor and an ozone generator rated at 5 g O3/h. Results show that ozone oxidation combined with activated carbon adsorption increases the overall BT oxidation rate with respect to the ozonation process and activated carbon adsorption. In the presence of free radical scavenger, only a 44% reduction in BT removal rate is observed in the simultaneous treatment, as compared with 72% when ozonation treatment is used, suggesting that BT oxidation reactions mainly take place on the activated carbon surface.     

Effect of Fe3O4 nanoparticles on magnetic xerogel composites for enhanced removal of fluoride and arsenic from aqueous solution

Fe₃O₄ magnetic xerogel composites were prepared by polycondensation of resorcinol (R)–formaldehyde reaction via a sol–gel process in an aqueous solution through varying the molar ratio of Fe₃O₄ nanoparticles (MNPs), catalyst (C), and water (W) content. MNPs were obtained by co-precipitation (MC), oxidation of iron salts (MO), or solvothermal synthesis (MS). Both MNPs and magnetic xerogels were examined regarding the performance of arsenic and fluoride removal in a batch system. The MC-based MNPs had higher adsorption capacities for both fluoride (202.9 mg/g) and arsenic (3.2 mg/g) than other MNPs in optimum conditions. The X-ray diffraction, Fourier transform infrared spectroscopy, and energy-dispersive X-ray spectroscopy confirmed that Fe was composed into the polymeric matrix of magnetic xerogels that contained 0.59%–4.42% of Fe with a molar ratio of MNPs (M) to R between 0.01 and 0.10. With low R/C and optimum M/R ratios, an increase in the surface area of magnetic xerogels affected the fluoride and arsenic adsorption capacities. The magnetic xerogel composites with the MC-based MNPs prepared at a fixed R/C ratio (100) and at different R/W (0.05–0.06) and M/R (0.07–0.10) ratios had a high arsenic removal efficiency of 100% at an As(V) concentration of 0.1 mg/L and pH of 3.0. The maximum adsorption capacities of magnetic xerogels were approximately five times higher than those of the xerogels without MNP composites. Therefore, Fe₃O₄ nanoparticles enhanced the adsorption of arsenate and fluoride. The variations of alkaline catalyst and water content significantly affected the resulting properties of textural and surface chemistry of magnetic xerogel composites.     

Four years of development and field-testing of IHE arsenic removal family filter in rural Bangladesh

UNESCO-IHE has been developing an arsenic removal family filter with a capacity of 100 L/day based on arsenic adsorption onto iron oxide coated sand, a by-product of iron removal plants. The longer term and field conditions performance of the third generation of eleven family filters prototypes were tested in rural Bangladesh for 30 months. All filters achieved initially highly effective arsenic removal irrespective of arsenic concentration and groundwater composition. Arsenic level in filtrate reached 10 mug/l after 50 days of operation at one testing site and after 18 months of continuous operation at other 3 testing sites. Arsenic level at other 7 sites remained below the WHO guideline value till the end of study. Positive correlation was found between arsenic removal capacity of the filter and iron concentration in groundwater. In addition to arsenic, iron present in groundwater at all testing sites was also removed highly effectively. Manganese removal with IHE family filter was effective only when treating groundwater with low ammonia. A simple polishing sand filter, after IHE family filter, resulted in consistent and effective removal of manganese. IHE family filters were easy to operate and were well accepted by the local population.     

Characterization of biofilm of a rotating biological contactor treating synthetic wastewater

A four-stage rotating biological contactor (RBC) was designed and operated to treat synthetic wastewater containing 1,000 mg/l chemical oxygen demand (COD) and 112 mg/l NH(4)(+)-N. A mixed culture bacterial biofilm was developed consisting of a heterotrophic bacterium Paracoccus pantotrophus, nitrifiers and other heterotrophs. Applying the peculiar characteristics of P. pantotrophus of simultaneous heterotrophic nitrification and aerobic denitrification, high simultaneous removal of carbon and nitrogen could be achieved in the fully aerobic RBC. The microbial community structure of the RBC biofilm was categorized based on the nitrate reduction, biochemical reactions, gram staining and morphology. The presence of P. pantotrophus within the RBC biofilm was confirmed with an array of biochemical tests. Isolates from the four stages of RBC were grouped into complete denitrifiers, incomplete denitrifiers and non-denitrifiers. This categorization showed a higher relative abundance of P. pantotrophus in the first stage as compared with subsequent stages, in which other nitrifiers and heterotrophs were significantly present. High total nitrogen removal of upto 68% was in conformity with observations made using microbial categorization and biochemical tests. The high relative abundance of P. pantotrophus in the biofilm revealed that it could successfully compete with other heterotrophs and autotrophic nitrifiers in mixed bacterial biomass.     

Removal of arsenic from aqueous solution by iron-coated sand and manganese-coated sand having different mineral types

In this study, the effects of the coating temperature during the preparation of manganese-coated sand (MCS) and iron-coated sand (ICS) on the removals of As(III) and As(V) were evaluated. The mineral type of manganese oxide on MCS-150, prepared at 150 °C, was identified as a mixture of pyrolusite and ramsdellite, which changed to high crystalline pyrolusite above 300 °C. The mineral type of ICS-150, prepared at 150 °C, was a mixture of goethite and hematite, which changed to high crystalline goethite above 300 °C. The adsorption efficiency was determined according to the mineral type which depended on the coating temperature. The As(III) oxidation efficiency of MCS-150 and As(V) adsorption efficiency of ICS-150 were approximately 77 and 70% higher compared with those of MCS-600 and ICS-600, respectively, prepared at 600 °C. Regardless of the coating temperature, the amounts of manganese and iron coated on the sand substrates were similar.     

Efficient nutrient removal from swine manure in a tubular biofilm photo-bioreactor using algae-bacteria consortia

Concentrated animals feeding operations (CAFOs) often pose a negative environmental impact due to the uncontrolled spreading of manure into soils that ends up in the release of organic matter and nutrients into water bodies. Conventional aerobic methods treating CAFOs wastewater require intensive oxygenation, which significantly increases the operational costs. The alternative proposed in this research is the application of micro-algae based systems by taking advantage of the cost-effective in situ oxygenation via photosynthesis. A 4.9 L enclosed tubular biofilm photo-bioreactor was inoculated with an algal-bacterial consortium formed by the micro-algae Chlorella sorokiniana and a mixed bacterial culture from an activated sludge process. C. sorokiniana delivers the O(2) necessary to accomplish both organic matter and ammonium oxidation. The reactor was fed with diluted swine wastewater containing 180, 15 and 2,000 mg/L of NH(4) (+)-N, soluble P and total COD, respectively. The photo-bioreactor exhibited good and sustained nutrient removal efficiencies (up to 99% and 86% for NH(4) (+) and PO(4) (3-), respectively) while total COD was removed up to 75% when the biofilm was properly established. Liquid superficial velocities up to 0.4 m/s (achieved by culture broth recirculation) hindered the formation of a stable biofilm, while operation at velocities lower than 0.1 m/s supported stable process performance. The high shear stress imposed by the centrifugal recirculation pump disintegrated the large aggregates detached from the biofilm, which resulted in a poor settling performance and therefore poor COD removal efficiencies. Enclosed biofilm photo-bioreactors therefore offer a potentially more economical alternative to conventional tertiary treatments process.     

Effect of chemical treatment on the acute toxicity of two commercial textile dye carriers.

In the present experimental study, the effect of chemical treatment (coagulation-flocculation) on the acute toxicity exerted by two commercial dye carriers (called Carrier A and B herein) often used in the textile industry was investigated. Two different test organisms were selected to elucidate the situations in activated sludge treatment systems (activated sludge microorganisms) as well as in receiving water bodies (ultimate marine discharge). According to the results of a comprehensive analysis covering COD removal efficiencies, sludge settling characteristics and operating costs involved in coagulation-flocculation, the optimum treatment conditions were defined as follows; application of 750 mg/L ferrous sulphate at a pH of 9.0 for Carrier A; and application of 550 mg/L ferrous sulphate at a pH of 9.0 for Carrier B. The acute toxicities of both dye carriers towards marine microalgea Phaeodactylum tricornutum could be reduced significantly after being subjected to coagulation-flocculation. Fair toxicity removals (towards heterotrophic mixed bacterial culture accommodated in activated sludge treatment) were obtained with coagulation-flocculation for both of the carriers under investigation.     

Arsenic contamination of groundwater in Nawabganj, Bangladesh, focusing on the relationship with other metals and ions.

Serious arsenic contamination of groundwater in Bangladesh has been frequently reported and is of great concern. In this research, repeated water sampling from the same 10 tubewells in Nawabganj municipality, Bangladesh, was conducted and analysed, focusing on the seasonal variation of water quality and the relationship among arsenic and other metals and ions. For the seasonal variation of water quality, arsenic and iron concentrations were higher in the rainy season in general although the tendency was not consistent and it depended on the tubewell and the time. Correlation between arsenic and iron could not be observed in this study (r = -0.01) when using all cases. This was because no correlation was observed in the higher arsenic concentration range. Arsenic removal by co-precipitation with coexisting iron is known as one of the locally applicable techniques in Bangladesh, but the result from this study suggests that some additional treatments such as the extra injection of iron should be performed in some cases, especially where the arsenic concentration is high. The correlation between arsenic and other substances was also analysed. As a result, manganese (r = 0.37), molybdenum (r = 0.33) and sulfate ion (r = -0.33) significantly correlated with arsenic (p < 0.05). The negative correlation between arsenic and sulfate ion implies the dissolution of arsenic into groundwater under reductive conditions although there are some exceptional cases.     

Comparative evaluation of As, Se and V removal technologies for the treatment of oil refinery wastewater

In this study, a broad range of readily deployable metal removal technologies were tested on a US refinery's wastewater to determine vanadium, arsenic and selenium removal performance. The bench-scale treatability studies were designed and performed so that test conditions could be as uniform as possible given the different mechanisms of action and engineering applications of each technology. The experimental data show that both ferric precipitation and reactive filtration were able to remove As, Se and V more efficiently from the wastewater than other tested technologies. Additionally, granular ferric hydroxide (GFH) adsorption was also effective in both V and As removal. Although the thiol-SAMMS adsorbent was developed for mercury removal, it also demonstrated appreciable selenium removal. None of the tested membrane filtration technologies showed any significant metals removal. This was attributed to the dissolved form of the metals as well as the wastewater's fouling characteristics.