猪骨/竹共热解生物炭对氨氮、Cd2+和Cu2+的吸附特性研究

为使用吸附法高效处理氨氮、Cd²⁺和 Cu²⁺混合污染废水,文章以猪骨、竹子为原料,采用共热解法制备骨竹生物炭;通过间歇吸附实验,研究混合比例、热解温度对共热解生物炭吸附性能的影响,同时探究了溶液条件对吸附过程的影响。结果表明,竹粉与骨粉质量比 1∶3,550 ℃制备的共热解生物炭 MC2 性能最优。MC2 对氨氮及 Cd²⁺、Cu²⁺的单一吸附数据 Langmuir 模型拟合最优,分别具有 13.97、108.11、153.54 mg/g 的吸附容量。动力学模型拟合表明,MC2 吸附 3 种污染物的过程符合准二级动力学模型。3 种污染物共存时,Cu²⁺竞争性大于 Cd²⁺,氨氮对 2 种金属离子无竞争性。     

不同生物炭对磷的吸附特征及其影响因素

为了实现植物生物质资源化利用,选择5种生物质材料制备生物炭,通过比较5种生物炭材料的磷吸附能力,筛选出了2种磷吸附效果较佳的材料,并探明了筛选生物炭材料的理化性质及其对磷的吸附特征.结果表明,5种生物炭材料中,仅水稻秸秆和玉米秸秆生物炭对磷具有吸附能力.Langmuir等温吸附曲线表明,水稻秸秆生物炭对废水中磷的吸附能力强于玉米秸秆生物炭,理论最大吸附量为：水稻秸秆生物炭(9.78 mg·g^-1)>玉米秸秆生物炭(0.39 mg·g^-1).水稻秸秆生物炭的比表面积(148.30 m²·g^-1)和总孔体积(0.11 cm³·g^-1)远高于玉米秸秆生物炭8.26 m²·g^-1和0.03 cm³·g^-1,同时水稻秸秆生物炭有更高的Mg、 Ca、 Fe和Al元素含量.水稻秸秆生物炭和玉米秸秆生物炭对磷吸附的最佳pH为酸性;在不同的pH范围内（3.0～11.0）,水稻秸秆生...     

生物炭固定耐镉菌群对Cd2+的吸附及作用机制

从广西某硫化尾矿中分离出一耐镉菌群,将其固定在生物炭上制成固定化菌剂.同时,探究了生物炭种类、添加量、溶液pH、Cd²⁺初始浓度对固定化菌剂吸附Cd²⁺性能的影响,并结合吸附动力学、吸附等温线、16S rDNA、SEM、FTIR、XPS等分析测试手段研究了固定化菌剂对Cd²⁺的吸附过程和作用机制.结果表明,竹生物炭制备的固定化菌剂(ZBCM)对Cd²⁺的吸附效果最佳,在Cd²⁺浓度为20 mg·L^-1、pH=6、生物炭投加量为3 g·L^-1的条件下,ZBCM对Cd²⁺的吸附率达89.49%,较生物炭和单菌群的吸附率分别提高了54.6%和53.51%.从属水平上看,菌群主要由梭状芽孢杆菌、毛梭菌和产己酸菌构成,ZBCM吸附Cd²⁺后优势菌变为副梭菌、毛梭菌和贪铜菌,贪铜菌丰度的增长增强了ZBCM对Cd²⁺的络合和生物积累作用.ZBCM对Cd²⁺的吸附...     

碳化温度对牛粪铜和锌形态及生态毒性的影响

通过设置不同的热解温度(350,550和750℃)对牛粪废弃物进行碳化处理,并使用光谱技术手段对牛粪炭的微观特点及Cu、Zn赋存形态进行了分析表征,同时结合淋溶和毒性实验探究了热解温度对牛粪炭生态毒性的影响.结果表明,高温碳化明显改善牛粪孔隙结构,使其比表面积从牛粪原料的1.15m²/g提高至牛粪炭的5.51(350℃)~195.90m²/g(750℃).随着热解温度的提高,牛粪炭pH值从8.18(350℃)提高到了10.14(750℃);牛粪炭中Cu、Zn含量则从牛粪原料中的1.22和1.23mg/g分别升高至18.29~35.11和18.58~31.24mg/g.透射电镜-选区衍射以及X射线能谱分析表明,热解处理可使牛粪中Cu、Zn离子分别转化为副黑铜矿(Cu₄O₃)和红锌矿(ZnO)等金属氧化物,从而明显降低了牛粪炭中水溶态、DTPA提取态以及HNO₃-H₂SO₄提取态的Cu、Zn离子浓度;此外,FTIR分析及混合有机酸浸提实验结果也表明,350℃牛粪炭中酚羟基、烷烃基、羧基、酰胺类等有机官能团通过吸附和络合作用固定未完全转化的Cu离子,而升高热解温度会使得这些官能团显著减少、促进Cu离子的完全转化以及无机物与Cu、Zn离子之间稳定金属氧化物化合键的形成.淋溶和生态毒性实验表明,高于550℃的热解温度能够显著降低牛粪炭中Cu、Zn的溶出率以及生态毒性,是高Cu、Zn含量牛粪废弃物无害化处理的一种推荐优选技术.     

硝酸改性显著提高花生壳生物炭对Cd2+的去除能力

本研究采用热分解的方法制备花生壳生物炭,并用乙醇、硝酸和高锰酸钾溶液对其进行改性。分别研究不同方法改性后生物炭吸附Cd²⁺的性能对初始浓度、吸附时间和pH的响应特征并通过吸附热力学和动力学探索吸附机理。结果表明,改性后的花生壳生物炭对Cd²⁺的吸附量和去除率明显提高。在花生壳投加量一定的情况下,综合分析得知硝酸改性后对Cd²⁺吸附效果最佳,吸附量为48.47 mg/g,去除率为96.94%。最佳条件为：Cd²⁺初始浓度200 mg/L,pH为7,吸附时间120 min。     

生物炭固定化解有机磷菌对Pb2+的吸附行为研究

分别在300、500和700℃将核桃青皮粉末限氧热解制备生物炭，以生物炭为载体固定化解有机磷菌(organic phosphorus-degrading bacteria, OPDB).通过对比不同热解温度生物炭固定化OPDB吸附Pb²⁺的效果，优选出吸附效果最佳的固定化OPDB菌剂.利用傅里叶变换红外光谱分析、扫描电子显微镜、比表面积测试法对其进行表征分析，并探讨了生物炭添加量、溶液pH和吸附温度对吸附行为的影响，结合吸附动力学与等温吸附模型探究生物炭固定化OPDB对Pb²⁺的吸附过程及机理.结果表明，500℃限氧热解核桃青皮生物炭固定化OPDB菌剂对Pb²⁺的吸附效果最佳，最适吸附条件为：温度30℃，pH为6～7，生物炭添加量为0.1 g·100 mL-1.吸附过程较符合拟一级动力学模型，且吸附30min基本达到平衡，符合Langmuir模型，属于单分子层吸附.     

KOH活化鱼鳞基生物炭的制备及其对VOCs的高效吸附去除研究

以废弃生物质罗非鱼鱼鳞为原料,用 KOH一步炭化活化法制备了鱼鳞基多孔生物炭,并借助 XRD、SEM、FTIR及 Boehm等方法对所制备生物炭的孔隙结构、形貌特征及表面化学性质进行表征 .结果表明：650 ℃条件下制备的生物炭（FSBC-1）表面含有最多的含氧基团,其中酚羟基含量为 0.3102 mmol·g^-1,而 850 ℃条件下制备的生物炭（FSBC-3）具备最高的比表面积(3370 m²·g^-1)和孔容(1.91 cm³·g^-1). 静态吸附实验表明,所制备生物炭对非极性分子甲苯的吸附过程符合 Langmuir模型,而 n-layer BET 模型能更好地描述材料对极性分子丙酮的吸附 .298 K条件下,FSBC-3 对 3 kPa 甲苯的吸附量高达 12.75 mmol·g^-1,对 20 kPa 丙酮的吸附量达 16.74 mmol·g^-1. 动态吸附实验和机理分析表明,对于低浓度VOCs,所制备生物炭对非极性分子甲苯的穿...     

不同原料生物炭的理化特性及其作炭基肥缓释载体的潜力评价

生物炭作炭基肥缓释载体的能力与其理化性质密切相关,因此在制备炭基肥前有必要对不同原料和热解温度制备的生物炭的理化性质进行评价.以苹果枝条、棉秆和杜仲枝条为原料,通过生物质干馏设备在400、 500、 600和700℃热解温度下制备生物炭,并对生物炭的pH、比表面积及孔隙结构、表面官能团和矿物组成等理化性质进行表征和灰色关联度分析,结合生产成本评价生物炭用于炭基肥缓释载体的潜力.结果表明,3种原料制备的生物炭的产率均随热解温度的升高而降低,其中400℃制备的苹果枝条生物炭的产率最高（37.4%）.所有生物炭的pH值均>10,表现出强碱性.在400～500℃热解温度范围内,苹果枝条、棉秆和杜仲枝条生物炭的比表面积和总孔容随温度的升高增大,最大比表面积分别为265.262 7、 107.449 1和316.185 4 m²·g^-1;当热解温度>500℃时,比表面积和总孔容减小.FTIR和XRD图谱分析表明,所有生物炭具有丰富的芳香结构,其中苹果枝条和棉秆生物炭含有较多的矿物组分,杜仲枝条生物炭为非晶生物炭.灰色关联分析表明当热解温度为5...     

磁性生物炭及其老化后对Cd2+的吸附性能影响

磁性生物炭(FBC)是一种具有良好吸附性能且可实现磁分离的吸附材料,但制备过程磁性前驱体用量及老化作用是否影响其结构和吸附重金属的能力却鲜有研究。以水稻秸秆和铁盐为原料制备不同铁炭质量比(1∶4、1∶2和1∶1,记作FBC-4、FBC-2、FBC-1)的FBC,比较其表面形态、官能团等理化性质,以及对Cd²⁺的吸附性能的差异;利用自然老化和高温老化2种物理方法研究老化作用对磁性生物炭理化性质和吸附性能的影响。结果表明：与普通生物炭(BC)相比,FBC具有更大的比表面积和孔容,含氧官能团数量增多,并且出现Fe—O的特征峰,FBC-4、FBC-2、FBC-1的饱和磁化强度随着单位生物炭载铁量增加而增大,分别为0.64、2.21和17.69 A·m²/kg;BC和FBC对Cd²⁺吸附等温线和动力学曲线均符合Langmuir方程和准二级动力学方程,拟合出的平衡吸附量和理论最大吸附量关系为FBC-1>FBC-4>FBC-2>BC,即磁改性可以提高对Cd²⁺的平衡吸附量,且FBC-1对Cd     

不同农作物秸秆原料制备生物炭特性及重金属浸出行为

采用水稻秆、大豆秆、小麦秆和玉米秆为原料在550℃缺氧条件下制备生物炭,考察不同原料生物炭理化性质及热解后重金属(Cr﹑Ni、 Cu﹑As﹑Cd和Pb)迁移转化特征,及其在不同浸出液中的浸出行为.结果表明,4种原料制备的生物炭的理化特性和元素组成基本一致,其中玉米秆生物炭微孔体积(0.006 cm³·g^-1)和比表面积(110.120 m²·g^-1)低于其他原料生物炭.秸秆热解后重金属(除Cd外)含量增加了14.04%～410.81%,且大部分重金属(除Cd和Pb外)化学形态由不稳定态(弱酸提取态和可还原态)向稳定态(可氧化态和残渣态)转化.制备的生物炭中的重金属在超纯水和缓冲盐溶液中无浸出或浸出量较少,在乙酸溶液和腐殖酸溶液中浸出量较高.其中Cu在乙酸溶液中浸出量较高,为2.601～4.224 mg·kg^-1,As在腐殖酸溶液中浸出量较高,介于0.074～0.166 mg·kg^-1.热解后,各种重金属的环境质量指数(PI_i)和内梅罗...     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.