Odours from pulp mill effluent treatment ponds: the origin of significant levels of geosmin and 2-methylisoborneol (MIB)

Pulp and paper mills are well known for their sharp, sulphurous stack emissions, but the secondary treatment units also can be significant contributors to local odour. This study investigated the source(s) of earthy/musty emissions from a mixed hardwood pulp mill in response to a high local odour. Samples from five sites in the mill over five months were analyzed for earthy/musty volatile organic compounds (VOCs), examined microscopically, and plated for bacteria and moulds. In all cases, activated sludge showed substantial geosmin levels and to a lesser extent 2-methylisoborneol (MIB) at 2000-9000 times their odour threshold concentrations (OTCs). These VOCs were lower or absent upstream and downstream, suggesting that they were produced within the bioreactor. Geosmin and MIB were highest in late summer and declined over winter, and correlated with different operating parameters. Geosmin was most closely coupled with temperature and MIB with nitrogen uptake. Cyanobacteria were present in all sludge samples, but actinomycetes were not found. Gram-negative bacteria and one fungal species isolated from the bioreactor and secondary outfall tested negative for geosmin or MIB. We conclude: (i) geosmin and MIB contribute significantly to airborne odours from this mill, but are diluted below OTC levels at the river; (ii) these VOCs are generated by biota in the activated sludge; and (iii) cyanobacteria are likely primary source(s). The growth of cyanobacteria in activated sludge represents a loss of energy to the heterotrophic population; thus earthy/musty odours may represent a diagnostic for less than optimal conditions.     

Fate of Mutagenicity Produced During Anaerobic Biodegradation of the Herbicide Chlornitrofen (CNP)

The mutagenicity of chlornitrofen (CNP)-containing solutions has been reported to increase during anaerobic biodegradation. In the present study, the fate of this increased mutagenicity under subsequent aerobic and anaerobic incubation conditions was investigated using two Salmonella tester strains, YG1024 (a frameshift-detecting strain) and YG1029 (a base-pair-substitution-detecting strain). Mutagenicity for both YG1024 and YG1029 strains increased during nine-day anaerobic biodegradation. During subsequent anaerobic incubation, the increased mutagenicity decreased gradually for YG1029 but did not change significantly for YG1024. By contrast, the increased mutagenicity decreased rapidly after the conversion to aerobic incubation for both YG1024 and YG1029 strains. The rapid decrease in mutagenicity during aerobic incubation was due to decreases, not only in an identified mutagenic metabolite (CNP-amino) but also in unidentified mutagenic metabolites.     

Biodegradation of pentaerythritol tetranitrate (PETN) by anaerobic consortia from a contaminated site

This study examined the role of denitrifying and sulfate-reducing bacteria in biodegradation of pentaerythritol tetranitrate (PETN). Microbial inocula were obtained from a PETN-contaminated soil. PETN degradation was evaluated using nitrate and/or sulfate as electron acceptors and acetate as a carbon source. Results showed that under different electron acceptor conditions tested, PETN was sequentially reduced to pentaerythritol via the intermediary formation of tri-, di- and mononitrate pentaerythritol (PETriN, PEDN and PEMN). The addition of nitrate enhanced the degradation rate of PETN by stimulating greater microbial activity and growth of nitrite reducing bacteria that were responsible for degrading PETN. However, a high concentration of nitrite (350 mg L⁻¹) accumulated from nitrate reduction, consequently caused self-inhibition and temporarily delayed PETN biodegradation. In contrast, PETN degraded at very similar rates in the presence and absence of sulfate, while PETN inhibited sulfate reduction. It is apparent that denitrifying bacteria possessing nitrite reductase were capable of using PETN and its intermediates as terminal electron acceptors in a preferential utilization sequence of PETN, PETriN, PEDN and PEMN, while sulfate-reducing bacteria were not involved in PETN biodegradation. This study demonstrated that under anaerobic conditions and with sufficient carbon source, PETN can be effectively biotransformed by indigenous denitrifying bacteria, providing a viable means of treatment for PETN-containing wastewaters and PETN-contaminated soils.     

Biodegradation and sorption of nodularin (NOD) in fine-grained sediments

Nodularin (NOD) is a cyclic pentapeptide hepatotoxin produced by the bloom forming cyanobacterium Nodularia spumigena. The fate of the toxin in the aquatic environment has not been fully evaluated. In the current study the changes in NOD concentration caused by biodegradation and sorption in samples from the Baltic were studied. Seawater of various salinities (0, 4, 8 and 12 PSU) and three forms of fine-grained sediment (sterile wet sediment, non-sterile wet sediment, and combusted sterile sediment) were incubated with 34.7 μg of NOD. The toxin was seen to be highly stable both in sterile and non-sterile seawater. During the 21-day experiment NOD concentrations in solutions overlying the combusted sediment and the sterile wet sediment were reduced to 12.5 ± 2.6% and 59.8 ± 2.4% of the initial value. The greatest loss of the toxin (up to 100%) was observed in the non-sterile seawater incubated with non-sterile wet sediment. These results indicate an important role of benthic microbial community in nodularin removal. Two biodegradation products with similar spectral characteristics to NOD were detected; one of which was identified as Adda amino acid.     

Application and appreciation of chemical sand fixing agent-poly (aspartic acid) and its composites

The sand fixing agent-poly (aspartic acid) (PASP) and its composites were applied in the field by two forms (spraying around by PASP solution and PASP powder directly). It was found that the sand fixing effect in powder form was not as good as in solution form, but it was more practical in dry region. It needed 9, 6 and 7 days for PASP, xanthan gum-PASP (X2) and ethyl cellulose-PASP (E3) to attain the maximal mechanical strength after they were applied, respectively. The sand fixing effect decreased when the material was subjected to repeated hydration-dehydration cycles and the material had no negative influence on plant growth. The PASP and its composites had water-retaining ability and could reduce the water evaporation.     

2,2-二氯乙烯基二甲基磷酸酯在TiO2/H2O界面上光催化降解

实验研究了２,２－二氯乙烯基二甲基磷酸酯在ＴｉＯ２／Ｈ２Ｏ界面上光催化降解的最适空气通入量,初始ＰＨ值, 不同浓度的调变性助催经剂Ｆｅ＾３＋、Ａｇ＾＋在供Ｏ２条件下对ＴｉＯ２光催化降解有机磷速率的影响。     

Hydrolysis of di-n-butyl phthalate, butylbenzyl phthalate and di(2-ethylhexyl) phthalate in human liver microsomes

Diester phthalates are industrial chemicals used primarily as plasticizers to import flexibility to polyvinylchloride plastics. In this study, we examined the hydrolysis of di-n-butyl phthalate (DBP), butylbenzyl phthalate (BBzP) and di(2-ethylhexyl) phthalate (DEHP) in human liver microsomes. These diester phthalates were hydrolyzed to monoester phthalates (mono-n-butyl phthalate (MBP) from DBP, mono-n-butyl phthalate (MBP) and monobenzyl phthalate (MBzP) from BBzP, and mono(2-ethylhexyl) phthalate (MEHP)) by human liver microsomes. DBP, BBzP and DEHP hydrolysis showed sigmoidal kinetics in V-[S] plots, and the Hill coefficient (n) ranged 1.37-1.96. The S₅₀, V_max and CL_max values for DBP hydrolysis to MBP were 99.7 μM, 17.2 nmol min⁻¹ mg⁻¹ protein and 85.6 μL min⁻¹ mg⁻¹ protein, respectively. In BBzP hydrolysis, the values of S₅₀ (71.7 μM), V_max (13.0 nmol min⁻¹ mg⁻¹ protein) and CL_max (91.3 μL min⁻¹ mg⁻¹ protein) for MBzP formation were comparable to those of DBP hydrolysis. Although the S₅₀ value for MBP formation was comparable to that of MBzP formation, the V_max and CL_max values were markedly lower (<3%) than those for MBzP formation. The S₅₀, V_max and CL_max values for DEHP hydrolysis were 8.40 μM, 0.43 nmol min⁻¹ mg⁻¹ protein and 27.5 μL min⁻¹ mg⁻¹ protein, respectively. The S₅₀ value was about 10% of DBP and BBzP hydrolysis, and the V_max value was also markedly lower (<3%) than those for DBP hydrolysis and MBzP formation for BBzP hydrolysis. The ranking order of CL_max values for monoester phthalate formation in DBP, BBzP and DEHP hydrolysis was BBzP to MBzP ? DBP to MBP > DEHP to MEHP > BBzP to MBP. These findings suggest that the hydrolysis activities of diester phthalates by human liver microsomes depend on the chemical structure, and that the metabolism profile may relate to diester phthalate toxicities, such as hormone disruption and reproductive effects.     

Migration of uranium(IV)/(VI) in the presence of humic acids in quartz sand: a laboratory column study

The migration behavior of U(IV) and U(VI) in the presence of humic acid was studied in a quartz sand system. Laboratory column experiments were performed using humic acid, U(VI) in humic acid absence, U(IV) and U(VI) in humic acid presence, and for comparison a conservative tracer. In experiments using humic acid, both redox species of U migrate nearly as fast as the conservative tracer. Humic acid accelerates the U(VI) breakthrough compared to the humic acid-free system. There are strong indications for a similar effect on the U(IV) transport. At the same time, a part of U(IV) and U(VI) associated with the humic acid is immobilized in the quartz sand due to humic colloid filtration thus producing a delaying effect. Tailing at a low concentration level was observed upon tracer elution. The experimental breakthrough curves were described by reactive transport modeling using equations for equilibrium and kinetic reactions. The present study demonstrates that humic acids can play an important role in the migration of actinides. As natural organic matter is ubiquitous in aquifer systems, the humic colloid-borne transport of actinides is of high relevance in performance assessment.     

蛭石在非缓冲与缓冲体系中的Zn~(2+)、Cd~(2+)吸附行为研究

探讨了蛭石分别在非缓冲体系与缓冲体系中的Zn2+、Cd2+吸附行为,比较了2个体系中Zn2+、Cd2+的平衡吸附量(qe),qe与平衡液相离子浓度(ce)、qe与ce和吸附剂浓度(W0)之比(ce/W0)的对应关系。结果表明,在非缓冲体系与缓冲体系中,在3个W0水平上,Zn2+、Cd2+都具有其独立的qe—ce等温吸附曲线,而qe与ce/W0具有良好的相关性,在3个W0水平上的qe—ce/W0等温吸附曲线基本拟合在一起,即在qe—ce/W0等温吸附曲线中均基本消除了吸附剂浓度效应;加入缓冲溶液的传统方法并不能消除W0对离子吸附效果的影响;缓冲体系中,大量的其他阳离子参与Zn2+、Cd2+的竞争吸附,从而使得Zn2+、Cd2+的qe相对降低;缓冲体系的qe—ce、qe—ce/W0等温吸附曲线与非缓冲体系相比,线性形式更为明显,缓冲体系的qe—ce/W0等温吸附曲线中,qe与ce/W0的对应关系没有非缓冲体系中的好。     

Dissipation of polycyclic aromatic hydrocarbons (PAHs) in the rhizosphere: Synthesis through meta-analysis

Polycyclic aromatic hydrocarbons (PAHs) are widespread and persistent organic pollutants with high carcinogenic effect and toxicity; their behavior and fate in the soil-plant system have been widely investigated. In the present paper, meta-analysis was used to explore the interaction between plant growth and dissipation of PAHs in soil based on the large body of published literature. Plants have a promoting effect on PAH dissipation in soils. There was no difference in PAH dissipation between soils contaminated with single and mixed PAHs. However, plants had a more obvious effect on PAH dissipation in freshly-spiked soils than in long-term field-polluted soils. Additionally, a positive effect of the number of microbial populations capable of degrading PAHs was observed in the rhizosphere compared with the bulk soil. Our meta-analysis established the importance of the rhizosphere effect on PAH dissipation in variety of the soil-plant systems.     

黄钠铁矾渣制备透明氧化铁黄的研究

研究了以黄钠铁矾渣为原料,采用滴加法制备透明铁黄的工艺条件,讨论了亚铁浓度、温度、通气量、搅拌速度及添加剂用量等因素对铁黄制备的影响.用XRD和TEM对产品进行表征.结果表明,铁黄粒子呈针状;长轴为95～125 nm,短轴为18～25 nm;无团聚现象,单分散性好.     

Degradation of rhodamine B by Fe(0)-based Fenton process with H2O2

Degradation of rhodamine B by Fe(0)-based Fenton process with H₂O₂ was investigated. The effects of H₂O₂ dose, Fe(0) dose, initial concentration of rhodamine B and initial pH value on the degradation of rhodamine B were examined. The results showed that the degradation and mineralization of rhodamine B occurred with low dose of H₂O₂ and Fe(0). The intermediates of rhodamine B were analyzed with UV-Vis spectrophotometry and ion chromatography and the mechanism of oxidative degradation of rhodamine B was also discussed. The reactive oxygen species (·OH) produced in Fe(0)-based Fenton process with H₂O₂ is the key to the degradation of rhodamine B by ways of N-de-ethylation, chromophore cleavage, ring-opening and mineralization.     

Reaction pathways of dimethyl phthalate degradation in TiO2-UV-O2 and TiO2-UV-Fe(VI) systems

The photocatalytic degradation of dimethyl phthalate (DMP) in aqueous TiO₂ suspension under UV illumination has been investigated using oxygen (O₂) and ferrate (Fe(VI)) as electron acceptors. The experiments demonstrated that Fe(VI) was a more effective electron acceptor than O₂ for scavenging the conduction band electrons from the surface of the catalyst. Some major intermediate products from DMP degradation were identified by HPLC and GC/MS analyses. The analytical results identified dimethyl 3-hydroxyphthalate and dimethyl 2-hydroxyphthalate as the two main intermediate products from the DMP degradation in the TiO₂–UV–O₂ system, while in contrast phthalic acid was found to be the main intermediate product in the TiO₂–UV–Fe(VI) system. These findings indicate that DMP degradation in the TiO₂–UV–O₂ and TiO₂–UV–Fe(VI) systems followed different reaction pathways. An electron spin resonance analysis confirmed that hydroxyl radicals existed in the TiO₂–UV–O₂ reaction system and an unknown radical species (most likely an iron–oxo species) is suspected to exist in the TiO₂–UV–Fe(VI) reaction system. Two pathway schemes of DMP degradation in the TiO₂–UV–O₂ and TiO₂–UV–Fe(VI) reaction systems are proposed. It is believed that the radicals formed in the TiO₂–UV–O₂ reaction system preferably attack the aromatic ring of the DMP, while in contrast the radicals formed in the TiO₂–UV–Fe(VI) reaction systems attack the alkyl chain of DMP.     

Geogenic Distribution of Arsenic (As) and Antimony (Sb) in Soils of the Murcia Region in Spain

The objective of this study was to determine the As and Sb contents in soils from the Murcia Region of Spain and the possible relationship between the mineralogical composition, soil properties, and As and Sb concentrations. In this study, 490 samples were selected from areas with different characteristics in order to study As and Sb variability. Results show that As and Sb concentrations are positively correlated with the phyllosilicate and quartz content but negatively correlated with the calcite content. The generic reference level (GRL) for these elements was determined according to the Spanish legislation. Established GRL values vary according to the established mineralogical groups, suggesting that GRL has to be determined considering the lithological characteristics of the study area.     

MB(A2/O)处理城市污水富磷上清液的化学除磷研究

为开发新型除磷脱氮工艺,研制了将MBR和A2/O工艺相结合的新型MB(A2/O)反应器。研究了MB(A2/O)反应器处理城市污水厌氧富磷上清液的化学除磷,并分析了过程机理及特性。结果表明：对于TP在30～45 mg/L的富磷上清液,采用含20% Ca(OH)2的工业石灰与P的最佳投加质量比为22.5;纯Ca(OH)2与P的最佳投加质量比为5.6（摩尔比为2.5）;FeSO4·7H2O与P的最佳投加质量比为10.7（Fe2＋与P的摩尔比为1.3）;Al2(SO4)3·12H2O与P的最佳投加质量比为12（Al3＋与P的摩尔比为1.3）时,均可使出水TP稳定在0.3 mg/L以下;以石灰、NaOH的联合投加方式可大幅减少石灰投加量。     

Factors influencing concentrations of dissolved gaseous mercury (DGM) and total mercury (TM) in an artificial reservoir

The effects of various factors including turbidity, pH, DOC, temperature, and solar radiation on the concentrations of total mercury (TM) and dissolved gaseous mercury (DGM) were investigated in an artificial reservoir in Korea. Episodic total mercury accumulation events occurred during the rainy season as turbidity increased, indicating that the TM concentration was not controlled by direct atmospheric deposition. The DGM concentration in surface water ranged from 3.6 to 160 pg/L, having a maximum in summer and minimum in winter. While in most previous studies DGM was controlled primarily by a photo-reduction process, DGM concentrations tracked the amount of solar radiation only in winter when the water temperature was fairly low in this study. During the other seasons microbial transformation seemed to play an important role in reducing Hg(II) to Hg(0). DGM increased as dissolved organic carbon (DOC) concentration increased (p-value < 0.01) while it increased with a decrease of pH (p-value < 0.01).     

COD、pH值和运行周期对好氧瞬时补料工艺合成聚羟基脂肪酸酯的影响

聚羟基脂肪酸酯（PHA）是一种可生物降解塑料,具有良好的应用前景。混合菌种生产PHA是目前PHA生产的研究重点。以乙酸钠为碳源用好氧瞬时补料（ADF）工艺驯化出了生产聚羟基脂肪酸酯（PHA）的混合菌种。PHA含量在加入营养液后4和10 h达到最大值。研究了营养液COD、pH值和SBR运行周期对PHA生产的影响。COD=12 000 mg·L-1和运行周期12 h均会引发污泥膨胀;COD=3 000 mg·L-1和运行周期48 h会导致污泥流失。pH=7的中性环境下PHA生产菌不具备竞争优势;pH=10时微生物细胞活性受抑制。最适条件为COD=6 000 mg·L-1,pH=8.5,运行周期=24 h,此时得到PHA含量最大值31.1%。     

盐酸羟胺和酒石酸强化Fe2+/Na2S2O8体系降解双酚A

Fe2+/Na2S2O8（persulfate,PS）体系中存在Fe2+易发生沉淀且Fe3+无法还原的问题,以典型的持久性有机污染物双酚A（bisphenol A,BPA）为研究对象,分别考察络合剂酒石酸（tartaric acid,TA）和还原剂盐酸羟胺（hydroxylamine,HA）强化Fe2+/PS体系对双酚A降解过程的影响。在Fe2+/TA/PS体系、Fe2+/HA /PS体系及Fe2+/TA/HA/PS体系中分别考察了盐酸羟胺投加量、酒石酸投加量、体系pH作用范围等因素的影响,同时对氧化作用机理加以分析。研究表明：酒石酸和盐酸羟胺均能提高双酚A在Fe2+/PS体系中的去除率,且均具有最优值;络合剂酒石酸起到长期促进作用,而还原剂盐酸羟胺起到短期促进作用。探针实验表明络合剂和还原剂共同强化的体系中·OH和SO4·-仍然是主要的氧化物种。当PS投加量均为2.64 mmol·L-1时,30 min内Fe2+/TA/HA/PS体系中SO4·-的生成量为11.3 μmol·L-1,而Fe2+/PS体系中SO4·-的生成量为1.4 μmol·L-1,表明体系通过加速了自由基生成速率从而加快了双酚A的降解。研究结果表明Fe2+/TA/HA/PS体系在中性条件下实现了对双酚A的强化降解,显著优于Fe2+/PS体系。     

Pseudomonas S2-3菌株对Cr(VI)的耐受性及去除

针对分离得到的Cr(VI)耐受菌株S2-3进行了基本生长特征、16S rRNA序列分析、Cr(VI)对菌株生长影响、菌株生长代谢与铬的去除的关系等研究。结果表明:该菌株属于假单胞菌,与Pseudomonas chlororaphis(Z76673)相似性最高(99.8%);Cr(VI)对菌株生长有着明显的抑制作用,其耐受上限可达到1500 mg/L左右;Cr(VI)导致菌体细胞大小分布变宽,同时使得细胞表面的-OH和-NH基团减少。当初始Cr(VI)浓度为100 mg/L时,48 h内菌株S2-3对Cr(VI)去除效率可达到85.9%,对总铬去除率为24.1%。在高Cr(VI)浓度(1000 mg/L)下,菌株对Cr(VI)和总铬仍有一定的去除效果,分别为58.7%和3.3%。菌株S2-3主要通过还原Cr(VI)的方式去除Cr(VI)。Cr(VI)的还原与菌液ORP以及细胞表面的-OH和-NH有关;总铬的去除不是因为形成了氢氧化铬沉淀,而是Cr(III)被吸附在了细胞表面的-C=O上。     

分子印迹型TiO2的制备及其对邻苯二甲酸二(2-乙基)己酯的光催化性能

以邻苯二甲酸二（2-乙基）己酯为模板分子、甲基丙烯酸为功能单体和乙二醇二甲基丙烯酸酯为交联剂,在TiO2表面合成DEHP分子印迹聚合物,制备了分子印迹型TiO2（MIP-TiO2）,优化了制备工艺条件。利用傅里叶红外光谱（FI-IR）和X-射线衍射（XRD）对MIP-TiO2进行表征,并考察了MIP-TiO2对DEHP的光催化降解性能。结果表明,MIP-TiO2的最佳制备工艺条件为模板分子、单体、交联剂和TiO2的摩尔比为1：4：10：1.875,反应温度为60 ℃;聚合时间为18 h。MIP-TiO2仍保持了和TiO2一样的锐钛矿型结构,对DEHP 的光催化效果明显高于TiO2,对浓度为5 mg·L-1的DEHP的光催化降解效率可达88.15%。