Methods to prepare biosorbents and magnetic sorbents for water treatment: a review

Access to drinkable water is becoming more and more challenging due to worldwide pollution and the cost of water treatments. Water and wastewater treatment by adsorption on solid materials is usually cheap and effective in removing contaminants, yet classical adsorbents are not sustainable because they are derived from fossil fuels, and they can induce secondary pollution. Therefore, biological sorbents made of modern biomass are increasingly studied as promising alternatives. Indeed, such biosorbents utilize biological waste that would otherwise pollute water systems, and they promote the circular economy. Here we review biosorbents, magnetic sorbents, and other cost-effective sorbents with emphasis on preparation methods, adsorbents types, adsorption mechanisms, and regeneration of spent adsorbents. Biosorbents are prepared from a wide range of materials, including wood, bacteria, algae, herbaceous materials, agricultural waste, and animal waste. Commonly removed contaminants comprise dyes, heavy metals, radionuclides, pharmaceuticals, and personal care products. Preparation methods include coprecipitation, thermal decomposition, microwave irradiation, chemical reduction, micro-emulsion, and arc discharge. Adsorbents can be classified into activated carbon, biochar, lignocellulosic waste, clays, zeolites, peat, and humic soils. We detail adsorption isotherms and kinetics. Regeneration methods comprise thermal and chemical regeneration and supercritical fluid desorption. We also discuss exhausted adsorbent management and disposal. We found that agro-waste biosorbents can remove up to 68–100% of dyes, while wooden, herbaceous, bacterial, and marine-based biosorbents can remove up to 55–99% of heavy metals. Animal waste-based biosorbents can remove 1–99% of heavy metals. The average removal efficiency of modified biosorbents is around 90–95%, but some treatments, such as cross-linked beads, may negatively affect their efficiency.

     

利用硫杆菌淋滤电镀污泥中的重金属(英文)

从广东云浮硫铁矿矿山酸性废水中分离得一株氧化亚铁硫杆菌(Thiobacillus ferrooxdans),从新兴县含硫化氢温泉中分离得一株氧化硫硫杆菌 (Thiobacillus thiooxidans), 并将其应用于电镀污泥的生物淋滤的研究,该污泥含铬、镍及铜分别为80.74 g/kg自然风干污泥、37.34g/kg自然风干污泥和13.42 g/kg自然风干污泥.利用未经驯化的氧化亚铁硫杆菌和氧化硫硫杆菌,以底物类型、菌液比、初始pH值和污泥浓度为四个因素,设置3个水平进行L9(34)正交实验,得出电镀污泥的最适淋滤条件:污泥浓度0.1%、硫酸亚铁和硫代硫酸钠作底物、菌液比T.f:T.t=:1:1、初始pH值2.0.为了将分离得的两种硫杆菌应用于更高浓度的电镀污泥,对所得菌进行驯化,以提高该菌种的重金属耐性,并应用于高浓度污泥的生物淋滤.经过驯化后的细菌,成功地适应了电镀污泥环境.结合上述最适条件,加入了合适的营养底物及还原剂之后,电镀污泥中的重金属,如铜、镍等,在30℃酸性好氧的环境中,能够在7天内被有效地淋滤出来,混合菌对污泥浓度为0.5%的污泥中铜的滤出率达90%以上,镍的滤出率40%以上;对1%的污泥的淋滤效果较差;对铬的淋滤效果不明显.本文还讨论了两株硫杆菌对高毒性电镀污泥的适应性.即在一定的污泥浓度范围内,氧化亚铁硫杆菌和氧化硫硫杆菌能够氧化底物,并产生硫酸将污泥中的重金属溶解,两株硫杆菌能够加快镍和铜的滤出效率.     

A feasibility study on bioelectrokinetics for the removal of heavy metals from tailing soil

The combination of bioremediation and electrokinetics, termed bioelectrokinetics, has been studied constantly to enhance the removal of organic and inorganic contaminants from soil. The use of the bioleaching process originating from Fe- and/or S-oxidizing bacteria may be a feasible technology for the remediation of heavy metal-contaminated soils. In this study, the bioleaching process driven by injection of S-oxidizing bacteria, Acidithiobacillus thiooxidans, was evaluated as a pre-treatment step. The bioleaching process was sequentially integrated with the electrokinetic soil process, and the final removal efficiency of the combined process was compared with those of individual processes. Tailing soil, heavily contaminated with Cd, Cu, Pb, Zn, Co, and As, was collected from an abandoned mine area in Korea. The results of geochemical studies supported that this tailing soil contains the reduced forms of sulfur that can be an energy source for A. thiooxidans. From the result of the combined process, we could conclude that the bioleaching process might be a good pre-treatment step to mobilize heavy metals in tailing soil. Additionally, the electrokinetic process can be an effective technology for the removal of heavy metals from tailing soil. For the sake of generalizing the proposed bioelectrokinetic process, however, the site-specific differences in soil should be taken into account in future studies.     

Preface

The combination of bioremediation and electrokinetics, termed bioelectrokinetics, has been studied constantly to enhance the removal of organic and inorganic contaminants from soil. The use of the bioleaching process originating from Fe- and/or S-oxidizing bacteria may be a feasible technology for the remediation of heavy metal–contaminated soils. In this study, the bioleaching process driven by injection of S-oxidizing bacteria, Acidithiobacillus thiooxidans, was evaluated as a pre-treatment step. The bioleaching process was sequentially integrated with the electrokinetic soil process, and the final removal efficiency of the combined process was compared with those of individual processes. Tailing soil, heavily contaminated with Cd, Cu, Pb, Zn, Co, and As, was collected from an abandoned mine area in Korea. The results of geochemical studies supported that this tailing soil contains the reduced forms of sulfur that can be an energy source for A. thiooxidans. From the result of the combined process, we could conclude that the bioleaching process might be a good pre-treatment step to mobilize heavy metals in tailing soil. Additionally, the electrokinetic process can be an effective technology for the removal of heavy metals from tailing soil. For the sake of generalizing the proposed bioelectrokinetic process, however, the site-specific differences in soil should be taken into account in future studies.     

Variations in heavy metal contamination of stream water and groundwater affected by an abandoned lead–zinc mine in Korea

This study evaluated variations in heavy metal contamination of stream waters and groundwaters affected by an abandoned lead–zinc mine, where a rockfill dam for water storage will be built 11 km downstream. For these purposes, a total of 10 rounds of stream and groundwater samplings and subsequent chemical analyses were performed during 2002–2003. Results of an exploratory investigation of stream waters in 2000 indicated substantial contamination with heavy metals including zinc (Zn), iron (Fe) and arsenic (As) for at least 6 km downstream from the mine. Stream waters near the mine showed metal contamination as high as arsenic (As) 8,923 μg L⁻¹, copper (Cu) 616 μg L⁻¹, cadmium (Cd) 223 μg L⁻¹ and lead (Pb) 10,590 μg L⁻¹, which greatly exceeded the Korean stream water guidelines. Remediation focused on the mine tailing piles largely improved the stream water qualities. However, there have still been quality problems for the waters containing relatively high concentrations of As (6–174 μg L⁻¹), Cd (1–46 μg L⁻¹) and Pb (2–26 μg L⁻¹). Rainfall infiltration into the mine tailing piles resulted in an increase of heavy metals in the stream waters due to direct discharge of waste effluent, while dilution of the contaminated stream waters improved the water quality due to mixing with metal free rain waters. Levels of As, Cu and chromium (Cr) largely decreased after heavy rain but that of Pb was rather elevated. The stream waters were characterized by high concentrations of calcium (Ca) and sulfate (SO₄), which were derived from dissolution and leaching of carbonate and sulfide minerals. It was observed that the proportions of Ca and SO₄ increased while those of bicarbonate (HCO₃) and sodium and potassium (Na+K) decreased after a light rainfall event. Most interestingly, the reverse was generally detected for the groundwaters. The zinc, being the metal mined, was the most dominant heavy metal in the groundwaters (1758–10,550 μg L⁻¹) near the mine, which far exceeded the Korean standard of 1000 μg L⁻¹ for drinking water. The decreases in the heavy metals contents in the groundwaters associated with reduced rainfall were quite different from the increases observed for the stream waters, which is not clearly understood at this time and warrants further investigation.     

纳米零价铁颗粒去除水中重金属的研究进展

重金属是毒性大、难降解、易累积的环境污染物,纳米零价铁作为一种新型功能修复材料在去除水体和土壤中重金属方面有着广阔的应用前景.本文综述了纳米零价铁颗粒去除水中重金属的研究进展,包括纳米零价铁的常用制备方法及特性、去除效能、对不同重金属的去除机理以及发展前景和今后的研究方向,以期为该领域的深入研究提供借鉴并拓展新的思路.     

Hydrochemical Monitoring and Heavy Metal Contaminations at the Narim Mine Creek in the Sulcheon District, Republic of Korea

The Narim gold mine is located approximately 200km southeast of Seoul within the Sulcheon mineralised district in the Yeongnam massif, Korea. In this study, environmental geochemical analyses were undertaken for soil, sediment and water samples collected in April, September and November in 1998 from the Narim mine creek. The mine area consists mainly of granitic gneiss; however, mineral constituents of soil and sediment near the mine were mainly composed of quartz, feldspar, mica, amphibole, some pyrite and clay minerals. Also were found some pyrite, arsenopyrite, chalcopyrite, sphalerite, galena, malachite, goethite, various hydroxide and unidentified secondary minerals. Generally, high concentrations of heavy metals in the soil and sediment are correlated with a high proportion of secondary minerals. Hydrochemical compositions of water samples are characterised by relative significant enrichment of Na⁺+K⁺ and alkali metals in the ground water, whereas the surface and mine waters are relatively enriched in Ca²⁺+Mg²⁺ and heavy metals. Anion contents of the ground waters are typically enriched in HCO₃ ^–, NO₃ ^– and Cl^–, whereas the surface and mine waters are highly enriched in HCO₃ ^– and SO₄ ^2–. The pH and EC values of the surface water from the non-mine creek are relatively lower compared with those of the surface water around the mine and waste dump. The range of D and ¹⁸O values (d parameters) of the water samples are shown in distinct two groups for the April waters of 10.1–13.1, and for the November waters of 5.8–7.9, respectively. This range variation indicates that two group water were composed of distinct waters because of seasonal difference. Geochemical modelling showed that mostly heavy toxic metals may exist largely in the form of free metal (M²⁺) and metal-sulphate (MSO₄ ^2–), and SO₄ ^2– concentration influenced the speciation of heavy metals in the mine water. These metals in the ground water could be formed of CO₃ ^– and OH^– complex ions. Using a computer program, saturation indices of albite, calcite, dolomite in mostly surface water show undersaturated and progressively evolved toward the saturation state, however, ground and mine waters are nearly saturated. The gibbsite, kaolinite and smectite are supersaturated in the surface and ground water, respectively. Calculated water-mineral reaction and stabilities suggest that the weathering of silicate minerals may be stable kaolinite. The clay minerals of K-illite and Na-smectite will be transformed to more stable kaolinite owing to the continuous reaction.     

Contamination by Cd, Cu, Pb, and Zn in mine wastes from abandoned metal mines classified as mineralization types in Korea

The objective of this study was to investigate heavy metal contamination and geochemical characteristics of mine wastes, including tailings, from 38 abandoned mines classified as five mineralization types. Mine waste materials including tailings and soils were sampled from the mines and the physical and chemical characteristics of the samples were analyzed. The particle size of tailings was in the range of 10–100 μm. The pH of the waste covered a wide range, from 1.73 to 8.11, and was influenced by associated minerals and elevated levels of Cd, Cu, Pb, and Zn, extracted by a Korean Standard Method (digestion with 0.1 mol L⁻¹ HCl), which were found in the wastes. Half of the samples contained heavy metals at levels above those stipulated by the Soil Environmental Conservation Act (SECA) in Korea. In addition, extremely high concentrations of the metals were also found in mine wastes extracted by aqua regia, especially those from mines associated with sulfide minerals. Thus, it can be expected that trace elements in mine wastes may be dispersed both downstream and downslope through water and wind. Eventually they may pose a potential health risk to residents in the vicinity of the mine. It is necessary to control mine wastes by using a proper method for their reclamation, such as neutralization of the mine wastes using a fine-grained limestone.     

Selective recovery of Cu, Zn, and Ni from acid mine drainage

In Korea, the heavy metal pollution from about 1,000 abandoned mines has been a serious environmental issue. Especially, the surface waters, groundwaters, and soils around mines have been contaminated by heavy metals originating from acid mine drainage (AMD) and mine tailings. So far, AMD was considered as a waste stream to be treated to prevent environmental pollutions; however, the stream contains mainly Fe and Al and valuable metals such as Ni, Zn, and Cu. In this study, Visual MINTEQ simulation was carried out to investigate the speciation of heavy metals as functions of pH and neutralizing agents. Based on the simulation, selective pH values were determined to form hydroxide or carbonate precipitates of Cu, Zn, and Ni. Experiments based on the simulation results show that the recovery yield of Zn and Cu were 91 and 94 %, respectively, in a binary mixture of Cu and Zn, while 95 % of Cu and 94 % of Ni were recovered in a binary mixture of Cu and Ni. However, the recovery yield and purity of Zn and Ni were very low because of similar characteristics of Zn and Ni. Therefore, the mixture of Cu and Zn or Cu and Ni could be recovered by selective precipitation via pH adjustment; however, it is impossible to recover selectively Zn and Ni in the mixture of them.     

酸阻滞技术的研究与应用

本文提出酸阻滞法从废液中分离，回收重金属和酸的新技术工艺，从十多种国产树脂中成功地筛选出两种可作为酸阻滞剂，有较好的分离效果。但洗脱时酸脱尾严重，当选择穿透比在０．６左右时，可以解决酸脱尾现象，使脱尾酸损失由３０％降到７％，而酸的回收率由６０％提高到９０％，采用该工艺对几种废液进行处理，重金属回收液中酸去除率大于９５％，而回用酸中金属去除率大于７０％，该工艺既可回收重金属，同时也可回收酸。     

In situ removal of arsenic from groundwater by using permeable reactive barriers of organic matter/limestone/zero-valent iron mixtures

In this study, two mixtures of municipal compost, limestone and, optionally, zero-valent iron were assessed in two column experiments on acid mine treatment. The effluent solution was systematically analysed throughout the experiment and precipitates from both columns were withdrawn for scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffractometry analysis and, from the column containing zero-valent iron, solid digestion and sequential extraction analysis. The results showed that waters were cleaned of arsenic, metals and acidity, but chemical and morphological analysis suggested that metal removal was not due predominantly to biogenic sulphide generation but to pH increase, i.e. metal (oxy)hydroxide and carbonate precipitation. Retained arsenic and metal removal were clearly associated to co-precipitation with and/or sorption on iron and aluminum (oxy)hydroxides. An improvement on the arsenic removal efficiency was achieved when the filling mixture contained zero-valent iron. Values of arsenic concentrations were then always below 10 μg/L.     

西藏当雄拉屋矿区污染土壤微生物及其活性研究

通过现场采样及室内培养分析,研究了西藏当雄拉屋矿区污染土壤微生物区系组成、主要生理类群及其活性。结果表明：矿区土壤受重金属Cu、Zn、Pb、Cd不同程度污染,矿区污染土壤几种重金属质量分数比非矿区土壤有明显的增加。矿区土壤微生物区系组成和各生理类群发生了明显变化,土壤细菌、真菌、放线菌以及各生理类群数量均显著降低,且3大微生物以及各生理类群对矿区污染的敏感性大小分别表现为放线菌〉细菌〉真菌,硝化细菌〉氨化细菌〉纤维分解菌。矿区土壤酶活性较低,对照土壤的各种酶活性最高,而矿区土壤基础呼吸和代谢商则受到刺激明显提高,其中土壤脱氢酶的活性变化最大,作为矿区重金属污染的指标更灵敏。可见,土壤中微生物区系组成及参与物质转化的生理类群种类、数量及土壤酶活和微生物活性在一定程度上可反映该矿区污染生境的重金属污染特征及其生态功能的演变规律。     

Modified dehydrogenase enzyme assay for evaluation of the influence of Hg,Cd, and Zn on the bacterial community structure of a wastewater treatment plant

In this study, a traditional assay was modified to evaluate the effect of Hg, Cd, and Zn on the bacterial community of a sequencing batch reactor and activated sludge plants and heavy metal-resistant bacterial species were determined. After the isolation of metal-resistant bacteria, their 16S rRNA gene fragments were sequenced. The BLAST program was used to compare the resulting 16S rRNA sequences with those in GenBank database to identify the isolated bacterial species. Hg was found to be the most toxic metal for both bacterial communities investigated. Sequence batch reactor bacteria were comparatively more resistant to Hg, Cd, and Zn than those from activated sludge. The resistant strains were close to the members of genus Pseudomonas, Kocuria, Stenotrophomonas, Enterococcus, and Staphylococcus. The modified dehydrogenase enzyme assay seems to be simple, robust, and competent for evaluation of the impact of metals on bacterial activity. Sequencing batch reactor systems should be preferred over activated sludge when wastewaters containing hazardous metals are to be treated.     

Removal of heavy metals by biosorption

Industrialization and urbanization have resulted in increased releases of toxic heavy metals into the natural environment comprising soils, lakes, rivers, groundwaters and oceans. Research on biosorption of heavy metals has led to the identification of a number of microbial biomass types that are extremely effective in bioconcentrating metals. Biosorption is the binding and concentration of adsorbate from aqueous solutions by certain types of inactive and dead microbial biomass. The novel types of biosorbents presently reviewed are grouped under fungal biomass, biomass of non-living, dried brown marine algae, agricultural wastes and residues, composite chitosan biosorbent prepared by coating chitosan, cellulose-based sorbents and bacterial strains. The reports discussed in this review collectively suggest the promise of biosorption as a novel and green bioremediation technique for heavy metal pollutants from contaminated natural waters and wastewaters.     

铅锌矿自然扩散晕内重金属的污染特征及其防治技术

研究了湖南省郴县东坡铅锌矿自然扩散晕内重金属的污染特征及污染控制措施，结果表明，该区域内的环境污染是以Ｐｂ、Ｚｎ、Ｃｄ和Ａｓ为主的多金属复合污染，污染物在土壤中的化学形态以残渣态为主，水体中的细微尾矿砂颗粒物是重金属的主要迁移载体。该区域内作物中的Ｐｂ、Ｃｄ残留很高，用改变耕种制度的方法来控制铅锌矿区内的重金属污染是有效的     

矿区周围土壤中重金属危害性评估研究

分别用总量法和连续萃取法对广东大宝山矿周围土壤、植物和沉积物中重金属的总量和化学形态进行了详细分析。结果发现，矿山废水流入的横石河沉积物中Pb、Zn、Cu和Cd的质量分数分别为1841．02、2326．28、1522．61和10.33mg／kg；经此河水灌溉的稻田中重金属(Cu、Cd、Pb和Zn)的质量分数也远远超出了土壤环境二级标准值，其中Cu、Cd超标倍数分别为14．01和4．17倍。结果还表明，生长在矿区周围的植物也受到不同程度重金属的污染且不同植物吸收和积累重金属的能力相差很大。用Tessier连续法对土壤中重金属进行萃取发现，虽然重金属主要存在于残余态中，但在Fe-Mn氧化态、有机结合态中的质量分数也很高．说明这些土壤确实受到了有毒有害重金属元素的严重污染。     

Association between heavy metals and antibiotic-resistant human pathogens in environmental reservoirs: A review

Heavy metals can act as co-selecting agents and promote antibiotic resistance. Most frequent resistances to heavy metals are observed for zinc and cadmium. P. aeruginosa and E. coli are commonly resistant to heavy metals and antibiotics. Heavy metals proliferate antibiotic resistance through co- and cross-resistance. Heavy metal and antibiotic resistances are common near anthropogenic activities. Antibiotic resistance in human pathogens can proliferate under selective pressures. Heavy metals in environmental reservoirs may contribute to selecting antibiotic-resistant strains. To determine the associations between heavy metals and antibiotic resistance, a literature review was conducted to systematically collect and categorize evidence for co-occurrence of resistance to heavy metals and antibiotics within human pathogenic bacteria in water, wastewater, and soil. In total, 42 publications adhered to inclusion criteria. Across the reservoirs, zinc and cadmium were the most commonly observed heavy metals associated with resistance to antibiotics. Pseudomonas aeruginosa and Escherichia coli were the most commonly studied bacteria with reported co-occurrence of resistance to several heavy metals and antibiotic classes. As co-selecting agents, prevalence of heavy metals in the environment can proliferate resistance to heavy metals and antibiotics through co-resistance and cross-resistance mechanisms. In comparing different reservoirs, soils and sediments harbor higher heavy metal and antibiotic resistances compared to water environments. Additionally, abiotic factors such as pH can affect the solubility and hence, the availability of heavy metals to bacterial pathogens. Overall, our review demonstrates heavy metals act as co-selecting agents in the proliferation of antibiotic resistance in human pathogens in multiple environmental reservoirs. More studies that include statistical data are needed to further describe the exposure-response relationships between heavy metals and antibiotic resistance in different environmental media. Moreover, integration of culture-based and molecular-based methods in future studies are recommended to better inform our understanding of bacterial co- and cross-resistance mechanisms to heavy metals and antibiotics.     

硫酸盐还原菌对酸性废水中重金属的生物沉淀作用研究

在小型连续搅拌槽式反应器（CSTR）中,研究了持续低pH条件下,硫酸盐还原菌的生物沉淀作用对人工配制酸性重金属废水的处理效果。试验设置反应器进水pH值依次为4-3,3．5和2．6三个处理,进水中Cu^2＋、Zn^2＋和Cr^3＋含量分别为65、36和10mg·L^-1,SO4^2-含量约为6200mg·L^-1,接种物为经耐酸驯化的混合硫酸盐还原菌,试验时控制水力停留时间为36h,通过定期测定反应器出水pH、氧化还原电位（ORP）、碱度、SO4^2、S^2-以及重金属含量变化等指标来考察废水生物沉淀的处理效果。研究结果表明：对于进水pH值为2．6～4.3的酸性重金属废水,硫酸盐还原菌的生物沉淀作用均有较好的处理效果。处理后,反应器出水pH值大幅升至6．5～8．0,碱度由起始的300～2000mg·L^-1增至7500-4600mg·L^-1,废水中S041-还原率达72％～80％,Cu^2＋和Zn^2＋的去除（沉淀）率达99．9％,Cr^3＋去除率达99．1％。此外,随着进水pH值由413降至2．6,反应器出水pH和碱度均呈现逐步下降的趋势,而S04}的生物还原和重金属的去除效果变化不大。从反应器运行稳定性考虑,控制酸性重金属废水的进水pH值为3．5较适宜今后的实际应用。     

The adsorption of lead and copper from aqueous solution on modified peat-resin particles

Raw peat was modified with sulfuric acid, then mixed modified with resin to prepare the modified peat-resin particles. Using the batch experimental systems, the removal of heavy metals (copper and lead) on the modified peat-resin particles was investigated. The data of the adsorption isotherm could be fitted by the Langmuir equation well. The adsorption rate of heavy metals on modified peat-resin particles was very swift. The removal processes of heavy metals on modified peat-resin particles could be well described by pseudo-second order model. The adsorption rate of lead was affected by the initial heavy metal concentration, initial pH, particle size, agitation speed and particle mass. In the adsorption of heavy metals (lead and copper) on the modified peat-resin particles, ion exchange was the major reaction mechanism. Desorption data showed that the lead adsorbed by modified peat-resin particle could be desorbed by 0.5 N or 1.0 N HNO3. The desorption rate was swift. The experiments indicated that the modified peat-resin particles have great potential for the removal of heavy metals from wastewater.     

碳酸盐岩矿区河流沉积物中重金属的形态特征及潜在生态风险

黔西北土法炼锌及铅锌选矿厂对河流造成严重的重金属污染。河流沉积物中重金属的化学形态研究表明,同一采样点中不同重金属的形态分布和同一重金属在不同采样点中的形态分布均有较大差异。这可能与沉积物组分的不同亲和力,不同河段沉积物中粘土矿物、有机质、Fe Mn氧化物含量的不同以及人为活动(生活污水、选矿剂、矿渣等)的加入等有关,而碳酸盐岩地质背景的河床本身可能也有较大影响。潜在生态危害指数法研究表明,沉积物中重金属表现出强生态风险性,产生生态危害的主要重金属污染物是Pb,其后依次是Cd、Cu和Zn。