Development and validation of abiotic ligand model for nickel toxicity to wheat (Triticum aestivum)

A terrestrial biotic ligand model (t-BLM) was developed to predict nickel toxicity to wheat (Triticum aestivum) root elongation in hydroponic solutions. The competitive effects of five major cations (Ca²⁺, Mg²⁺, Na⁺, K⁺ and H⁺) on Ni toxicity were investigated and Mg²⁺ was found to be a strong competitor, while H²⁺ showed less competing effect. Besides free Ni²⁺, the toxicity induced by the species NiHCO₃⁺ was non-neglect able at pH > 7 because NiHCO₃⁺ occupied a significant fraction of total Ni under such condition. Thus, a t-BLM including Ni²⁺, NiHCO₃⁺, Mg²⁺, and H⁺ could successfully predict the nickel toxicity to wheat root elongation and it performed better prediction than the conventional free ion activity model. In addition, the model was examined with two sets of independent experiments, which contained multiple cations and low-molecular-weight organic acids to mimic the rhizo-sphere condition. The developed t-BLM well predicted nickel toxicity in both experiments since it can account in both complexation and competition effects, suggesting its potential to be used in a complicated matrix like soil solution. This study provides direct evidence that the t-BLM is a reliable method for the risk assessment of nickel in terrestrial system.     

The biological effect of metal ions on the granulation of aerobic granular activated sludge

As a special biofilm structure, microbial attachment is believed to play an important role in the granulation of aerobic granular activated sludge (AGAS). This experiment was to investigate the biological effect of Ca^2 +, Mg^2 +, Cu^2 +, Fe^2 +, Zn^2 +, and K⁺ which are the most common ions present in biological wastewater treatment systems, on the microbial attachment of AGAS and flocculent activated sludge (FAS), from which AGAS is always derived, in order to provide a new strategy for the rapid cultivation and stability control of AGAS. The result showed that attachment biomass of AGAS was about 300% higher than that of FAS without the addition of metal ions. Different metal ions had different effects on the process of microbial attachment. FAS and AGAS reacted differently to the metal ions as well, and in fact, AGAS was more sensitive to the metal ions. Specifically, Ca^2 +, Mg^2 +, and K⁺ could increase the microbial attachment ability of both AGAS and FAS under appropriate concentrations, Cu^2 +, Fe^2 +, and Zn^2 + were also beneficial to the microbial attachment of FAS at low concentrations, but Cu^2 +, Fe^2 +, and Zn^2 + greatly inhibited the attachment process of AGAS even at extremely low concentrations. In addition, the acylated homoserine lactone (AHL)-based quorum sensing system, the content of extracellular polymeric substances and the relative hydrophobicity of the sludges were greatly influenced by metal ions. As all these parameters had close relationships with the microbial attachment process, the microbial attachment may be affected by changes of these parameters.     

Application of internal standard method in recombinant luminescent bacteria test

Mercury and its organic compounds have been of severe concern worldwide due to their damage to the ecosystem and human health. The development of effective and affordable technology to monitor and signal the presence of bioavailable mercury is an urgent need. The Mer gene is a mercury-responsive resistant gene, and a mercury-sensing recombinant luminescent bacterium using the Mer gene was constructed in this study. The mer operon from marine Pseudomonas putida strain SP1 was amplified and fused with prompterless luxCDABE in the pUCD615 plasmid within Escherichia coli cells, resulting in pTHE30–E. coli. The recombinant strain showed high sensitivity and specificity. The detection limit of Hg^2 + was 5 nmol/L, and distinct luminescence could be detected in 30 min. Cd^2 +, Cu^2 +, Zn^2 +, Ca^2 +, Pb^2 +, Mg^2 +, Mn^2 +, and Al^3 + did not interfere with the detection over a range of 10^− 5–1 mM. Application of recombinant luminescent bacteria testing in environmental samples has been a controversial issue: especially for metal-sensing recombinant strains, false negatives caused by high cytotoxicity are one of the most important issues when applying recombinant luminescent bacteria in biomonitoring of heavy metals. In this study, by establishing an internal standard approach, the false negative problem was overcome; furthermore, the method can also help to estimate the suspected mercury concentration, which ensures high detection sensitivity of bioavailable Hg^2 +.     

模拟酸雨对水稻叶片质膜H~+-ATPase活性与矿质元素含量的影响

采用水培法研究模拟酸雨(p H=5.0、3.5、2.5)对水稻叶片质膜H+-ATPase活性与矿质元素含量的影响.结果显示:与对照(CK)相比,酸雨处理5 d(胁迫期)后,p H=5.0组质膜H+-ATPase活性与活化能、K+、Ca2+、Mg2+含量均无显著变化,仅细胞渗透势下降.p H=3.5酸雨导致细胞渗透势、K+含量下降,质膜H+-ATPase活性、H+-ATPase活化能、Ca2+含量明显上升,Mg2+含量无显著变化.p H=2.5组H+-ATPase活性、细胞渗透势和K+、Mg2+含量明显下降,H+-ATPase活化能和Ca2+含量上升,表明矿质元素含量不仅受H+-ATPase活性的调控,还与酸雨强度和离子价态有关.经5 d恢复(恢复期)后,p H=5.0组各指标均恢复到CK水平,p H=3.5组除细胞渗透势外均恢复至CK水平,p H=2.5处理组各指标虽未达到CK水平,但较胁迫期有所恢复.表明K+、Ca2+、Mg2+含量受H+-ATPase活性的调节,且恢复效果受酸雨强度影响.     

Phosphate recovery from anaerobic digester effluents using CaMg(OH)4

Dolomite lime(DL)(CaMg(OH)_4) was used as an economical source of Mg~(2+)for the removal and recovery of phosphate from an anaerobic digester effluent of a municipal wastewater treatment plant(MWWTP) wastewater. Batch precipitation results determined that phosphate was effectively reduced from 87 to less than 4 mg-P/L when the effluent water was mixed with 0.3 g/L of DL. The competitive precipitation mechanisms of different solids in the treatment system consisting of Ca~(2+)–Mg~(2+)–NH_4~+–PO_4~(3-)CO_3~(2-)were determined by comparing model predictions with experimental results. Thermodynamic model calculations indicated that hydroxyapatite(Ca_(10)(PO_4)_6(OH)_2), Ca_4H(PO_4)_3?3H_2O, Ca_3(PO_4)_2(beta), and Ca_3(PO_4)_2(am2)were more stable than struvite(MgNH_4PO_3?6H_2O) and calcite(CaCO_3). However, X-ray diffraction(XRD) analysis determined the formation of struvite and calcite minerals in the treated effluent. Kinetic experimental results showed that most of the phosphate was removed from synthetic effluent containing NH_4~+within 2 hr, while only 20% of the PO_4~(3-)was removed in the absence of NH_4~+after 24 hr of treatment. The formation of struvite in the DL-treated effluent was due to the rapid precipitation rate of the mineral. The final pH of the DL-treated effluent significantly influenced the mass ratio of struvite to calcite in the precipitates. Because more calcite was formed when the p H increased from 8.4 to 9.6, a p H range of 8.0–8.5 should be used to produce solid with high PO_4~(3-)content. This study demonstrated that DL could be used for effective removal of phosphate from the effluent and that resultant precipitates contained high content of phosphate and ammonium.     

Japanese Papilio butterflies puddle using Na+ detected by contact chemosensilla in the proboscis

Many butterflies acquire nutrients from non-nectar sources such as puddles. To better understand how male Papilio butterflies identify suitable sites for puddling, we used behavioral and electrophysiological methods to examine the responses of Japanese Papilio butterflies to Na⁺, K⁺, Ca²⁺, and Mg²⁺. Based on behavioral analyses, these butterflies preferred a 10-mM Na⁺ solution to K⁺, Ca²⁺, and Mg²⁺ solutions of the same concentration and among a tested range of 1?mM to 1?M NaCl. We also measured the ion concentrations of solutions sampled from puddling sites in the field. Na⁺ concentrations of the samples were up to 6?mM, slightly lower than that preferred by butterflies in the behavioral experiments. Butterflies that sipped the 10?mM Na⁺ solution from the experimental trays did not continue to puddle on the ground. Additionally, butterflies puddled at sites where the concentrations of K⁺, Ca²⁺, and/or Mg²⁺ were higher than that of Na⁺. This suggests that K⁺, Ca²⁺, and Mg²⁺ do not interfere with the detection of Na⁺ by the Papilio butterfly. Using an electrophysiological method, tip recordings, receptor neurons in contact chemosensilla inside the proboscis evoked regularly firing impulses to 1, 10, and 100?mM NaCl solutions but not to CaCl₂ or MgCl₂. The dose?Cresponse patterns to the NaCl solutions were different among the neurons, which were classified into three types. These results showed that Japanese Papilio butterflies puddle using Na⁺ detected by the contact chemosensilla in the proboscis, which measure its concentration.     

Effects of metal ions on the catalytic degradation of dicofol by cellulase

A new technique whereby cellulase immobilized on aminated silica was applied to catalyze the degradation of dicofol, an organochlorine pesticide. In order to evaluate the performance of free and immobilized cellulase, experiments were carried out to measure the degradation efficiency. The Michaelis constant, K_m, of the reaction catalyzed by immobilized cellulase was 9.16 mg/L, and the maximum reaction rate, V_max, was 0.40 mg/L/min, while that of free cellulase was K_m = 8.18 mg/L, and V_max = 0.79 mg/L/min, respectively. The kinetic constants of catalytic degradation were calculated to estimate substrate affinity. Considering that metal ions may affect enzyme activity, the effects of different metal ions on the catalytic degradation efficiency were explored. The results showed that the substrate affinity decreased after immobilization. Monovalent metal ions had no effect on the reaction, while divalent metal ions had either positive or inhibitory effects, including activation by Mn^2 +, reversible competition with Cd^2 +, and irreversible inhibition by Pb^2 +. Ca^2 + promoted the catalytic degradation of dicofol at low concentrations, but inhibited it at high concentrations. Compared with free cellulase, immobilized cellulase was affected less by metal ions. This work provided a basis for further studies on the co-occurrence of endocrine-disrupting chemicals and heavy metal ions in the environment.     

Removal of Cs from water and soil by ammonium-pillared montmorillonite/Fe3O4 composite

To remove cesium ions from water and soil, a novel adsorbent was synthesized by following a one-step co-precipitation method and using non-toxic raw materials. By combining ammonium-pillared montmorillonite (MMT) and magnetic nanoparticles (Fe₃O₄), an MMT/Fe₃O₄ composite was prepared and characterized. The adsorbent exhibited high selectivity of Cs⁺ and could be rapidly separated from the mixed solution under an external magnetic field. Above all, the adsorbent had high removal efficiency in cesium-contaminated samples (water and soil) and also showed good recycling performance, indicating that the MMT/Fe₃O₄ composite could be widely applied to the remediation of cesium-contaminated environments. It was observed that the pH, solid/liquid ratio and initial concentration affected adsorption capacity. In the presence of coexisting ions, the adsorption capacity decreased in the order of Ca^2 + > Mg^2 + > K⁺ > Na⁺, which is consistent with our theoretical prediction. The adsorption behavior of this new adsorbent could be expressed by the pseudo-second-order model and Freundlich isotherm. In addition, the adsorption mechanism of Cs⁺ was NH₄⁺ ion exchange and surface hydroxyl group coordination, with the former being more predominant.     

Effect of organic matter on phosphorus recovery from sewage sludge subjected to microwave hybrid pretreatment

Microwave (MW) hybrid processes are able to disrupt the flocculent structure of complex waste activated sludge, and help promote the recovery of phosphorus as struvite. In this study, to optimize struvite yield, (1) the characteristics of matter released in MW-hybrid treatments were compared, including MW, MW-acid, MW-alkali, MW-H₂O₂, and MW-H₂O₂-alkali. The results showed that selective release of carbon, nitrogen, phosphorus, Ca^2 +, and Mg^2 + achieved by sludge pretreatment using MW-hybrid processes. MW-H₂O₂ is the recommended sludge pretreatment process for phosphorus recovery in the form of struvite. The ratio of Mg^2 +:NH₄⁺-N:PO₄^3 −-P was 1.2:2.9:1 in the supernatant. (2) To clarify the effects of organic matter on struvite recovery, the composition and molecular weight distribution of organic matters were analyzed. Low molecular weight COD was found to facilitate the removal rate of NH₄⁺-N and PO₄³-P via crystallization, and the amorphous struvite crystals (< 1 kDa) from the filtered solutions had high purity. Therefore, the present study reveals the necessity of taking into consideration the interference effect of high molecular weight organic matters during struvite crystallization from sewage sludge.     

Biodegradation of pendimethalin by Bacillus subtilis Y3

A bacterium strain Y3,capable of efficiently degrading pendimethalin,was isolated from activated sludge and identified as Bacillus subtilis according to its phenotypic features and 16 S rRNA phylogenetic analysis.This strain could grow on pendimethalin as a sole carbon source and degrade 99.5%of 100 mg/L pendimethalin within 2.5 days in batch liquid culture,demonstrating a greater efficiency than any other reported strains.Three metabolic products,6-aminopendimethalin,5-amino-2-methyl-3-nitroso-4-(pentan-3-ylamino) benzoic acid,and 8-amino-2-ethyl-5-(hydroxymethyl)-1,2-dihydroquinoxaline-6-carboxylic acid,were identified by HPLC-MS/MS,and a new microbial degradation pathway was proposed.A nitroreductase catalyzing nitroreduction of pendimethalin to 6-aminopendimethalin was detected in the cell lysate of strain Y3.The cofactor was nicotinamide adenine dinucleotide phosphate(NADPH) or more preferably nicotinamide adenine dinucleotide(NADH).The optimal temperature and pH for the nitroreductase were 30℃ and 7.5,respectively.Hg~(2+),Ni~(2+),Pb~(2+),Co~(2+),Mn~(2+) Cu~(2+),Ag~+,and EDTA severely inhibited the nitroreductase activity,whereas Fe~(2+),Mg~(2+),and Ca~(2+) enhanced it.This study provides an efficient pendimethalin-degrading microorganism and broadens the knowledge of the microbial degradation pathway of pendimethalin.     

Chemical characteristics of acidified waters in southwest China

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不同植被类型及土壤对径流水化学特征的影响

在不同植被类型覆盖条件下,对降雨形成地表径流和地下径流的化学成分变化及其与土壤剖面性质的关系进行分析,结果表明:地表径流和地下径流的化学特征与雨水基本相同,阳离子主要以Ca²⁺为主,离子排序为Ca²⁺>K⁺>Na⁺>Mg²⁺>NH₄⁺,阴离子以SO₄^2-为主,SO₄^2->NO₃^->Cl^-.降雨形成地表径流和地下径流后,各成分浓度发生了明显的变化,水体中主要的阴阳离子如Ca²⁺、Mg²⁺、K⁺、Na⁺、SO₄^2-、Cl^-等浓度增加,与雨水相比为内贮型化学成分,地下径流中Ca²⁺、Mg²⁺、SO₄^2-和Cl^-增加的幅度显著高于地表径流.相关分析结果显示,地下径流pH受到土壤pH的强烈影响,受土壤胶体吸附的影响,水体中Ca²⁺、Mg²⁺、K⁺、Na⁺等阳离子与土壤交换性阳离子之间一般呈负相关的关系,由于阴离子容易随水流失,水体中SO₄^2-、NO₃^-和Cl^-与土壤相关离子之间普遍呈正相关关系.     

The research of below-cloud scavengingof rainwater in Guilin City

Ｔｈｅｒｅｓｅａｒｃｈｏｆｂｅｌｏｗ－ｃｌｏｕｄｓｃａｖｅｎｇｉｎｇｏｆｒａｉｎｗａｔｅｒｉｎＧｕｉｌｉｎＣｉｔｙＢａｉＹｕｈｕａ；ＹａｏＲｏｎｇｋｕｉ；ＬｉＸｉｎ；ＴａｎｇＸｉａｏｙａｎ（ＴｈｅＤｅｐａｒｔｍｅｎｔｏｆＴｅｃｈｎｉｃａｌＰｈｙｓｉｅ...     

Atmospheric dry deposition on pines in the Eastern Brook Lake Watershed,Sierra Nevada,California

Atmospheric dry deposition to branches of Pinus contorta and P. albicaulis was measured during summer 1987 in a sub-alpine zone at Eastern Brook Lake Watershed (EBLW), eastern Sierra Nevada, California. Results are presented as deposition fluxes of NO₃⁻, SO₄²⁻, PO₄³⁻, Cl⁻, F⁻, NH₄⁺, Ca²⁺, Mg²⁺, Na⁺, K⁺, Zn²⁺, Fe³⁺, Mn²⁺, Pb²⁺ and H⁺, and compared with other locations in California and elsewhere. Deposition fluxes of anions and cations to the pine branches were low, several times lower than the values determined near the Emerald Lake Watershed (ELW), another sub-alpine location in the western Sierra Nevada. The sums of deposition fluxes of the measured cations and anions to pine surfaces were similar, in contrast to the ELW location where the sums of cation fluxes were much higher than the sums of anion fluxes. A strong positive correlation between depositions of NO₃⁻ and NH₄⁺, as well as SO₄²⁻ and Ca²⁺, suggested that large portions of these ions might have originated from particulate NH₄NO₃ and CaSO₄ deposited on pine surfaces. An estimated total N dry deposition (surface deposition of NO₃⁻ and NH₄⁺ and internal uptake of NO₂ and HNO₃) to the forested area of the EBLW was 29.54 eq ha⁻¹ yr⁻ (about 414 g H ha⁻¹ yr⁻¹).     

Chemical composition of rain in Thessaloniki,Greece, in relation to meteorological conditions

Wet precipitation was collected in Thessaloniki, Greece, during the period March 1989–December 1990 by using an automatic wet-only precipitation sampler.Rainwater samples were analysed for major cations (H⁺, NH₄⁺, Na⁺, K⁺, Ca²⁺, Mg²⁺) and anions (Cl⁻, NO₃⁻, SO₄²⁻), in addition to acidity and conductivity measurements. The majority of rain had a neutral or alkaline character as a result of neutralization, primarily caused by calcareous soil dust and secondarily by atmospheric ammonia. In all rain, SO₄²⁻ concentration exceeded NO₃⁻ concentration. The contribution of maritime sources to the total SO₄²⁻ concentration was very low (<2%).The chemical composition of precipitation was analysed in conjunction with meteorological variables (season of the year, precipitation type, airflow patterns) to evaluate temporal variations and chemical source influence. Rain caused by weak, localized flows showed the highest acidity and the minimum influence of neutralization processes.     

沙尘天气对兰州市PM10中主要水溶性离子的影响

利用在线监测仪器MARGA在兰州大学盘旋路校区对兰州市大气PM10中水溶性离子进行监测,监测期间(2011-04-01~2011-06-30)有15 d出现沙尘天气.兰州市PM10中主要水溶性离子物种为Ca2+、SO2-4和NO-3.扬沙天气期间NO-3和NH+4的浓度比非沙尘期间低,说明沙尘天气对当地人为源所排放污染物具有清除作用.沙尘天气期间,作为土壤污染源标识物的Mg2+、Na+和Ca2+离子都有明显增加,Na+和Mg2+相关系数为0.520,Na+和Ca2+相关系数为0.659,Mg2+和Ca2+相关系数为0.671,而非沙尘天气期间三者的相关系数并不高,Na+和Mg2+相关系数为0.065,Na+和Ca2+相关系数为0.131,Mg2+和Ca2+相关系数为0.163,说明沙尘天气期间三者之间具有相同的污染源,主要来自于土壤风沙尘,而非沙尘天气期间三者来源不同.Cl-的浓度在扬沙天气明显高于浮尘和非沙尘天气期间,说明外来的土壤风沙尘是Cl-的主要来源.     

Quantum chemical investigation on photodegradation mechanisms of sulfamethoxypyridazine with dissolved inorganic matter and hydroxyl radical

Sulfamethoxypyridazine(SMP) is one of the commonly used sulfonamide antibiotics(SAs).SAs are mainly studied to undergo triplet-sensitized photodegradation in water under natural sunlight with other coexisting aquatic environmental organic pollutants.In this work,SMP was selected as a representative of SAs.We studied the mechanisms of triplet-sensitized photodegradation of SMP and the influence of selected dissolved inorganic matter,i.e.,anions(Br~-,Cl~-,and NO~-_3) and cations ions(Ca~(2+),Mg~(2+),and Zn~(2+)) on SMP photodegradation mechanism by quantum chemical methods.In addition,the degradation mechanisms of SMP by hydroxyl radical(OH·) were also investigated.The creation of SO_2 extrusion product was accessed with two different energy pathways(pathway-1 and pathway-2) by following two steps(step-I and step-II) in the tripletsensitized photodegradation of SMP.Due to low activation energy,the pathway-1 was considered as the main pathway to obtain SO_2 extrusion product.Step-II of pathway-1 was measured to be the rate-limiting step(RLS) of SMP photodegradation mechanism and the effect of the selected anions and cations was estimated for this step.All selected anions and cations promoted photodegradation of SMP by dropping the activation energy of pathway-1.The estimated low activation energies of different degradation pathways of SMP with OH·radical indicate that OH·radical is a very powerful oxidizing agent for SMP degradation via attack through benzene derivative and pyridazine derivative ring.     

Kinetics of nitrobenzene degradation coupled to indigenous microorganism dissimilatory iron reduction stimulated by emulsified vegetable oil

Widespread contamination by nitrobenzene(NB) in sediments and groundwater requires better understanding of the biogeochemical removal process of the pollutant. NB degradation, coupled with dissimilatory iron reduction, is one of the most efficient pollutant removal methods. However, research on NB degradation coupled to indigenous microorganism dissimilatory iron reduction stimulated by electron donors is still experimental. A model for remediation in an actual polluted site does not currently exist.Therefore, in this study, the dynamics was derived from the Michaelis–Menten model(when the mass ratio of emulsified vegetable oil and NB reached the critical value 91:1). The effect of SO_4~(2-), NO_3~-, Ca~(2+)/Mg~(2+), and the grain size of aquifer media on the dynamics were studied, and the NB degradation dynamic model was then modified based on the most significant factors. Utilizing the model, the remediation time could be calculated in a contaminated site.     

浙江宁波天童地区酸性降水化学特征研究

为了解浙江宁波天童地区降水的化学特征、离子来源及酸性降水的成因,于2010年3月—2011年2月在该地区采集了90个降水样品,并运用离子色谱法分析其化学组分.结果显示,天童地区降水的酸化频率和酸化程度非常高,酸雨频率为97%,雨量加权pH平均值为4.37,离子浓度的大小顺序为SO24->NH4+>NO3->Ca2+>Cl->Na+>Mg2+>K+>F-,降水较清洁;降水pH值和各离子含量存在明显的季节变化,总体表现为冬、春季污染程度高于夏、秋季;SO24-/NO3-的浓度比值为1.9,表明该地区酸雨类型为硫酸和硝酸复合型;SO24-、NO3-、NH4+和部分Ca2+主要来自人为污染源,Na+、Cl-和大部分Mg2+主要来自海洋源,K+和大部分Ca2+则主要来自地壳源,海洋对天童地区降水离子组分影响较大,但对降水酸度影响并不显著;NH4+与SO42-(r=0.90)、NO3-(r=0.88)的相关性分别大于Ca2+与SO24-(r=0.67)、NO3-(r=0.73)的相关性,且NH4+/Ca2+的浓度比值为1.47,说明NH4+对降水酸性的中和作用大于Ca2+,与我国其他城市降水相比,天童地区降水中的碱性离子,尤其是Ca2+浓度较低,从而导致降水酸度高于北方地区和西南其他地区.