Comparison of the complexation potential of extracellular polymeric substances (EPS), extracted from activated sludges and produced by pure bacteria strains, for cadmium, lead and nickel

This paper provides information on the metal complexation potential of extracellular polymeric substances (EPS), extracted from activated sludges and from eight pure cultures of bacteria isolated from the same activated sludge. The EPS extracted from pure bacteria cultures are mainly composed of proteins and low quantities of polysaccharides and uronic acids in comparison with EPS extracted from activated sludges. The EPS studied present two apparent pK(a) and the IR spectra show the presence of the same functional groups on all the EPS studied. The ability of EPS to complex Cd, Pb and Ni, was studied at pH 7 with Chau and Ruzic's models using polarography titration. All of the EPS exhibited a greater ability to complex Pb than Ni, Cd showing the weakest affinity overall. The EPS extracted from the pure cultures of bacteria were less able to complex the metals than that extracted from activated sludges. Literature data, IR data and EPS phosphorous content, supported by the EPS pK(a), revealed that carboxylic and phosphoric groups may play a major role in binding to metals at pH 7. This study underlines the importance of metal exposure in order for bacteria to secrete or modify EPS. After exposure, the EPS then exhibit the greatest capacity to bind metal in order to protect bacteria from harmful effects of heavy metals.     

Lead and cadmium biosorption by extracellular polymeric substances (EPS) extracted from activated sludges: pH-sorption edge tests and mathematical equilibrium modelling

The sorption of Cd and Pb by extracellular polymeric substances (EPS) extracted from activated sludges originated from wastewater treatment plants (WWTPs) or Lab-scale bioreactors was investigated as a function of pH. The study was carried out using a polarographic method in the SMDE (stripping mercury dropping electrode) mode which is suited to determine labile metals in solution containing soluble ligands such as EPS. The results obtained provide evidence of the presence of a pH-sorption/desorption edge for Cd and Pb by EPS. The use of Kurbatov’s model gives information on the mechanisms involved through the determination of “relative complexation constants” (operationally defined) and the number of protons exchanged. The use of this model demonstrates that proton exchange with metals is not the only mechanism involved in metal biosorption by EPS. Other mechanisms such as cation exchange with Ca or Mg, global electric field surrounding the ligand or micro-precipitation of metals could be involved in metal sorption by EPS. The position of the pH-sorption edge curves and the “relative complexation constants” show that Pb displays a greater affinity for EPS than Cd. The studied EPS have large differences regarding binding strength of Cd and Pb. These differences are not correlated with the organic parameters measured to characterize the EPS, however the mineral fraction of the EPS could be involved to a large extent in the sorption of metal.     

不同提取方法对活性污泥胞外聚合物吸附废水中Cd(Ⅱ)效能的影响

为了比较不同提取方法对胞外聚合物(EPS)的提取及其吸附Cd(Ⅱ)的影响,考察了pH、单一物理提取方法和组合方法对脱水污泥中EPS的提取量及其对Cd(Ⅱ)的吸附能力的影响。结果表明：碱性条件在能够提高EPS提取量的同时,也能够提高EPS对Cd(Ⅱ)的吸附能力;不同物理处理方法对EPS的提取效率影响顺序为加热法>超声法>离心法,但其对Cd(Ⅱ)的吸附能力影响顺序为超声法>离心法>加热法;组合物理方法虽然较单一方法的EPS提取效率要高,但其提取EPS吸附Cd(Ⅱ)的能力较单一方法弱。以上结果可为EPS重金属吸附剂的有效提取和工业化应用提供参考。     

Inhibition of rainbow trout acetylcholinesterase by aqueous and suspended particle-associated organophosphorous insecticides

Cadmium (Cd) adsorption on 14 non-calcareous New Jersey soils was investigated with a batch method. Both adsorption edge and isotherm experiments were conducted covering a wide range of soil composition, e.g. soil organic carbon (SOC) concentration ranging from 0.18% to 7.15%, and varying Cd concentrations and solution pH. The SOC and solution pH were the most important parameters controlling Cd partition equilibrium between soils and solutions in our experimental conditions. The Windermere humic aqueous model (WHAM) was used to calculate Cd adsorption on soils. The effect of solution chemistry (various pH and Cd concentrations) on Cd adsorption can be well accounted for by WHAM. For different soil compositions, SOC concentration is the most important parameter for Cd binding. Only a fraction of SOC, the so-called active organic carbon (AOC), is responsible for Cd binding. We found a linear relationship between SOC and AOC based on the adsorption edge data. The linear relationship was validated by the independent data sets: adsorption isotherm data, which presumably can be used to predict Cd partition equilibrium across a wide range of soil compositions. The modeling approach presented in this study helps to quantitatively predict Cd behavior in the environment.     

Enhancement of exopolysaccharides production and reactive oxygen species level of Nostoc flagelliforme in response to dehydration

Environmental Science and Pollution Research - Nostoc flagelliforme is a remarkable drought-resistant terrestrial cyanobacterium whose exopolysaccharides (EPS) have been found to exert important...     

Characterization and cadmium-resistant gene expression of biofilm-forming marine bacterium Pseudomonas aeruginosa JP-11

Biofilm-forming marine bacterium Pseudomonas aeruginosa JP-11 was isolated from coastal marine sediment of Paradeep Port, Odisha, East Coast, India, which resisted up to 1,000 ppm of cadmium (Cd) as cadmium chloride in aerobic conditions with a minimal inhibitory concentration of 1,250 ppm. Biomass and extracellular polymeric substances (EPS) secreted by the cells effectively removed 58.760?±?10.62 and 29.544?±?8.02 % of Cd, respectively. The integrated density of the biofilm-EPS observed under fluorescence microscope changed significantly (P?≤?0.05) in the presence of 50, 250, 450, 650 and 850 ppm Cd. ATR-FTIR spectroscopy showed a peak at 2,365.09/cm in the presence of 50, 250, 450 and 650 ppm Cd which depicts the presence of sulphydryl group (–SH) within the EPS, whereas, a peak shift to 2,314.837/cm in the presence of 850 ppm Cd suggested the major role of this functional group in the binding with cadmium. On exposure to Cd at 100, 500 and 1,000 ppm, the expression profiles of cadmium resistance gene (czcABC) in the isolate showed an up-regulation of 3.52-, 17- and 24-fold, respectively. On the other hand, down-regulation was observed with variation in the optimum pH (6) and salinity (20 g l^?1) level. Thus, the cadmium resistance gene expression increases on Cd stress up to the tolerance level, but an optimum pH and salinity are the crucial factors for proper functioning of cadmium resistance gene.     

污泥生物沥滤工艺优化和重金属分配研究

为了得到嗜酸硫细菌沥滤污泥中重金属的最佳工艺参数,对沥滤过程进行3因素4水平的正交实验研究。3种影响因素的水平设置分别为:污泥浓度35、25、15和5 g/L,单质硫投加量15、10、5和1 g/L,接种量15、10、5和3 g/L。对沥滤过程污泥中7种重金属(As、Cd、Cr、Cu、Ni、Pb和Zn)的去除率进行极差分析,提出了因素影响程度依次为单质硫投加量污泥浓度接种量,且最佳工艺条件为:污泥浓度25 g/L,单质硫投加量10 g/L,接种量为5%。采用超声波-离心方法,分步提取污泥胞外聚合物(EPS)的2种形态:松散结合态(LB)和紧密结合态(TB)。分析其中的重金属浓度,提出沥滤后重金属在污泥EPS的赋存以LB为主。     

改性多壁碳纳米管对水中Cd2+的去除

为了增加多壁碳纳米管(multiwall carbon nanotubers,MWNTs)对水中Cd2+的吸附量,使用混酸对多壁碳纳米管进行氧化处理,采用红外光谱进行结果表征,并探讨了吸附时间、pH值和MWNTs的使用量、Cd2+的浓度及干扰离子对镉离子吸附的影响。结果表明,吸附时间为1.5 h、pH为5.3、吸附效果最佳,随MWNTs量的增加Cd2+去除量增加,共存的阳离子会降低对Cd2+的吸附效果,对Cd2+的吸附符合Longmuir吸附定律。研究同时表明,pH小于2时Cd2+能容易从碳纳米管上解吸。初步探讨了Cd2+吸附机制。     

低浓度Pb2+、Cd2+对鲫鱼肝脏组织中 HSP70诱导的影响

以鲫鱼(Carassius auratus)作为实验对象,经过40 d Pb2+、Cd2+不同浓度的暴露后,运用SDS-PAGE和Western Blotting方法检测鱼肝脏组织内应激蛋白HSP70的诱导表达情况.结果表明,在实验浓度下,与对照组相比,Pb2+、Cd2+对鱼肝脏内HSP70有显著的诱导(P＜0.05),但在Cd2+浓度为0.2 mg/L有停止表达HSP70的现象,可能是由于浓度过高造成了组织病理损伤而破坏了诱导表达机制.实验还发现,在实验浓度低于国家渔业用水标准时,HSP70仍然表现为明显诱导(P＜0.05),充分说明运用分子生物学指标要比传统的环境检测指标敏感,具有对污染物早期预警的作用.     

羟肟酸功能化PMMA/AM/HOA的合成及对Hg2+和Cd2+的吸附性能

用悬浮聚合法合成了甲基丙烯酸甲酯（MMA）与丙烯酰胺（AM）的共聚物PMMA/AM,再经羟胺改性制备了含羟肟酸功能基的改性PMMA/AM/HOA 树脂。通过红外光谱（FTIR）和热重分析（TG）对PMMA/AM/HOA树脂的结构和稳定性进行了表征。以PMMA/AM/HOA为吸附剂,考察了温度、吸附时间、pH值和金属离子浓度等条件对Hg2+、Cd2+两种金属离子吸附性能的影响。结果表明,改性树脂对Hg2+、Cd2+具有良好的吸附能力,其实验吸附量分别为0.822和0.384 mmol·g-1。改性树脂对Hg2+和Cd2+的吸附过程符合拟二级动力学方程,25℃时其二级动力学吸附速率常数分别为5.301×10-2和3.582×10-2 g·（mmol·min）-1;改性树脂对Hg2+和Cd2+的吸附量随温度的升高有所增大,吸附过程符合Langmuir和Freundlich吸附等温式。     

Role of extracellular compounds in Cd-sequestration relative to Cd uptake by bacterium Sinorhizobium meliloti

The role of bacterially derived compounds in Cd(II) complexation and uptake by bacterium Sinorhizobium meliloti wild type (WT) and genetically modified ExoY-mutant, deficient in exopolysaccharide production, was explored combining chemical speciation measurements and assays with living bacteria. Obtained results demonstrated that WT- and ExoY-strains excreted siderophores in comparable amounts, while WT-strain produced much higher amount of exopolysaccharides and less exoproteins. An evaluation of Cd(II) distribution in bacterial suspensions under short term exposure conditions, showed that most of the Cd is bound to bacterial surface envelope, including Cd bound to the cell wall and to the attached extracellular polymeric substances. However, the amount of Cd bound to the dissolved extracellular compounds increases at high Cd(II) concentrations. The implications of these findings to more general understanding of the Cd(II) fate and cycling in the environment is discussed.     

血粉对废水中镉离子的高效去除效应

以屠宰场废弃动物血液为原料,经高温干燥、粉碎为血粉,以此血粉为吸附剂,研究血粉添加量、溶液初始浓度、吸附温度、溶液pH、吸附时间对废水中Cd2+吸附量与去除率的影响。结果表明,在25℃、pH=5时,4 g血粉对初始浓度为20 mg·L-1的镉离子溶液（100 mL）振荡吸附2 h后,溶液中剩余镉离子浓度为0.1 mg·L-1,Cd2+的去除率为99.38%,达到污水综合排放标准（GB 8978-1996）中镉排放限值0.1 mg·L-1;血粉对镉离子的吸附反应符合Langmuir等温吸附方程,可决系数为0.999 7,Cd2+的理论饱和吸附量为10.24 mg·g-1。为了使剩余Cd2+浓度达到更低（电镀废水排放标准）,在吸附工艺上设计出2步吸附法,即第1次吸附后的混合液进行过滤,再将滤液加1 g血粉进行第2次吸附。结果表明,2步吸附法大大降低了溶液中剩余Cd2+离子浓度,即经过第1步、第2步吸附后,溶液中剩余Cd2+离子浓度降至0.006 mg·L-1,达到或低于电镀污染物排放标准（GB 21900-2008）对Cd2+的排放限值（0.05 mg·L-1）。这是常规吸附剂活性炭、石英砂、高岭土等所不能达到的技术指标,为废水去除Cd2+提供了一种可能的新技术。     

狭叶香蒲活性炭对Cd2+与Pb2+的吸附及机理分析

为了解狭叶香蒲(Typha angustifolia L.)活性炭的吸附性能及其机理,采用磷酸一步活化法制备了狭叶香蒲活性炭,并对其理化性质进行了表征;通过静态实验,研究了溶液起始pH、Cd2+和Pb2+浓度、吸附时间、温度、活性炭剂量对狭叶香蒲活性炭吸附水溶液中Cd2+和Pb2+的影响。狭叶香蒲活性炭对Cd2+和Pb2+的吸附量随溶液起始pH与温度的增加而增加,吸附平衡时间约为10 min;热力学分析表明,吸附过程自发而且吸热,吸附动力学实验结果符合拟二级动力学模型, Langmuir吸附等温模型能更好地拟合狭叶香蒲活性炭对Cd2+的吸附, Pb2+的平衡吸附量与Freundlich模型的拟合性更好。25℃条件下,由Langmuir线性模型拟合得到的Cd2+和Pb2+最大吸附量Qm分别为83.33和116.28 mg/g。狭叶香蒲活性炭的理化性质分析表明,活性炭表面凹凸不平、多孔,比表面积为780.42 m2/g、孔容23.29 mL/g、平均孔径3.14 nm;活性炭含有羟基、磷酸基、C[FY=, 1]C键等,等电点为3.3。结果表明,狭叶香蒲活性炭是Cd2+和Pb2+吸附的有效吸附剂,吸附过程包括静电吸附、离子交换等。     

Ca2+对生物膜形态结构及其组分的影响

通过向序批式生物膜反应器(SBBR)中投加Ca2+,考察Ca2+对生物膜形态结构及其组分的影响,探究Ca2+在生物膜形成中的作用影响规律及其对生物膜反应器运行的影响,以期能为含钙废水处理及优化废水处理效果提供理论指导。研究结果表明,Ca2+浓度增加有助于生物膜形成,并提高生物膜结构致密性;连续少量增加Ca2+(1~2 mg/L)有助于挂膜初期(约10 d)有机物去除;然而Ca2+浓度过高则会抑制生物膜活性,影响其降解性:当Ca2+浓度超过120 mg/L时,氨氮去除率出现下降,当Ca2+浓度超过280 mg/L时,有机物和总氮去除率显著下降。对生物膜及其胞外多聚物(EPS)组分的分析表明,Ca2+不会刺激微生物分泌产生更多EPS,但会导致生物膜干重增加。     

Characterization of the interactions between tetracycline antibiotics and microbial extracellular polymeric substances with spectroscopic approaches

The antibiotics have attracted global attentions for their impact on aquatic ecosystem. The knowledge about the fate of antibiotics encountering extracellular polymeric substances (EPS) is, however, limited. In this study, we investigated the interacting mechanisms of tetracycline (TC) to EPS extracted from aerobic activated sludge. The contributions of the main components of EPS, extracellular proteins, and polysaccharides were evaluated using bovine serum albumin and alginate sodium, respectively. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and nuclear magnetic resonance indicated that hydroxyl, carboxyl, and amino groups were the domain chemical groups involved in the interaction between TC and EPS, and the binding of TC onto EPS changed the structure of these chemical groups, thus causing shifts in their UV–visible absorption spectra. In addition, we found that extracellular proteins, rather than polysaccharides, were the major active contents involved in the interaction. Three-dimensional excitation–emission matrix fluorescence spectroscopy showed that the fluorophores in EPS were clearly quenched by TC and the static quenching process was observed, implying the complex formation of TC and EPS. Furthermore, thermodynamic analysis indicated that the binding of TC with EPS is spontaneous and dominated by electrostatic forces.     

Effects of pH, Fe, and Cd on the uptake of Fe2+ and Cd2+ by rice

The rhizosphere plays an important role in altering cadmium (Cd) solubility in paddy soils and Cd accumulation in rice. However, more studies are needed to elucidate the mechanism controlling rice Cd solubility and bioavailability under different rhizosphere conditions to explain the discrepancy of previous studies. A rice culture with nutrient solution and vermiculite was conducted to assess the effects of pH, Eh, and iron (Fe) concentration on Cd, Fe fractions on the vermiculite/root surface and their uptake by rice. The solution pH was set from 4.5 to 7.5, with additions of Fe (30 and 50 mg L^?1) and Cd (0.5 and 0.9 mg L^?1). At pH 5.5, the Eh in the rice rhizosphere was higher whereas transpiration, Cd²⁺, and Fe²⁺ adsorption on the vermiculite/root surface and accumulation in rice were lower than the other pH treatments. Cadmium addition had no impact on pH and Eh in rice rhizosphere while Fe addition decreased pH and increased Eh significantly. Compared with control, Fe addition resulted in the decrease of rhizosphere Cd, Fe solubility and bioavailability. Higher redox potential in the rice rhizosphere resulted in the decline of transpiration, Cd, and Fe accumulation in the rice tissues, suggesting that the transfer of two elements from soil to rice was depressed when the rhizosphere was more oxidized.     

Methane oxidation and formation of EPS in compost: effect of oxygen concentration

Oxygen concentration plays an important role in the regulation of methane oxidation and the microbial ecology of methanotrophs. However, this effect is still poorly quantified in soil and compost ecosystems. The effect of oxygen on the formation of exopolymeric substances (EPS) is as yet unknown. We studied the effect of oxygen on the evolution of methanotrophic activity. At both high and low oxygen concentrations, peak activity was observed twice within a period of 6 months. Phospholipid fatty acid analysis showed that there was a shift from type I to type II methanotrophs during this period. At high oxygen concentration, EPS production was about 250% of the amount at low oxygen concentration. It is hypothesized that EPS serves as a carbon cycling mechanism for type I methanotrophs when inorganic nitrogen is limiting. Simultaneously, EPS stimulates nitrogenase activity in type II methanotrophs by creating oxygen-depleted zones. The kinetic results were incorporated in a simulation model for gas transport and methane oxidation in a passively aerated biofilter. Comparison between the model and experimental data showed that, besides acting as a micro-scale diffusion barrier, EPS can act as a barrier to macro-scale diffusion, reducing the performance of such biofilters.     

Influence of extracellular polymeric substances (EPS) on Cd adsorption by bacteria

The role of extracellular polymeric substances (EPS) in Cd adsorption by Bacillus subtilis and Pseudomonas putida was investigated using a combination of batch adsorption experiments, potentiometric titrations, Fourier transform infrared spectroscopy (FTIR). An increased adsorption capacity of Cd was observed for untreated bacteria relative to that for EPS-free bacteria. Surface complexation modeling of titration data showed the similar pK_a values of functional groups (carboxyl, phosphate and hydroxyl) between untreated and EPS-free bacteria. However, site concentrations on the untreated bacteria were found to be higher than those on the EPS-free bacteria. FTIR spectra also showed that no significant difference in peak positions was observed between untreated and EPS-free bacteria and carboxyl and phosphate groups were responsible for Cd adsorption on bacterial cells. The information obtained in this study is of fundamental significance for understanding the interaction mechanisms between heavy metals and biofilms in natural environments.     

Metal binding properties of extracellular polymeric substances extracted from anaerobic granular sludges

Extracellular polymeric substances (EPS) were extracted from four anaerobic granular sludges with different procedures to study their involvement in biosorption of metallic elements. EPS extracts are composed of closely associated organic and mineral fractions. The EPS macromolecules (proteins, polysaccharides, humic-like substances, nucleic, and uronic acids) have functional groups potentially available for the binding of metallic elements. The acidic constants of these ionizable groups are: pK _a1 (4–5) corresponding to the carboxyl groups; pK _a2 (6–7) corresponding to the phosphoric groups; pK _a3 (8–10) and pK _a4 (≈10) corresponding to the phenolic, hydroxyl, and amino groups. The polarographic study confirms the higher affinity of the EPS to bind to lead than to cadmium. Moreover, the binding of these metallic compounds with the EPS is a mix of several sorption mechanisms including surface complexation, ion exchange, and flocculation. Inorganic elements were found as ions linked to organic molecules or as solid particles. The mineral fraction affects the binding properties of the EPS, as the presence of salts decreases the EPS binding ability. Calcite and apatite particles observed on SEM images of EPS extracts can also sorb metallic elements through ion exchange or surface complexation.