Mineralization of Catechol by Fenton and Photo‐Fenton Processes

Catechol is one of the most abundant phenolic components of olive mill wastewaters. In this article, the mineralization of this compound in synthetic aqueous solutions by the Fenton and photo‐Fenton processes is studied. It has been found that for 1.44 mM catechol, the total organic carbon of solutions is reduced about 94.4% at best after 60 min of Fenton treatment at optimized conditions of pH 3.0, 0.2 mM Fe²⁺, 7.09 mM H₂O₂, and 25°C. A faster and overall mineralization is attained by applying photo‐Fenton with UVA irradiation. o‐Benzoquinone, 1,2,3‐trihydroxybenzene and 1,2,4‐trihydroxybenzene were identified by GC–MS as primary quinonic and polyhydroxylated derivatives. Small amounts of generated carboxylic acids like muconic, maleic, malonic, acetic, oxalic, and formic acids were detected by ion‐exclusion chromatography. The Fe(III) complexes of these acids persist in the medium under Fenton conditions, while their photolysis by UVA light and that of other by‐products account for by the faster degradation and total mineralization achieved in the photo‐Fenton process. A reaction sequence for catechol mineralization by Fenton and photo‐Fenton involving all intermediates detected is proposed.     

Spinel Ferrite Mediated Photo‐Fenton Degradation of Phenolic Analogues: A Detailed Study Employing Two Distinct Inorganic Oxidants

The present work demonstrates the applicability of ferrites as photo‐Fenton catalysts for deterioration of different phenolic derivatives. To analyze optimal reaction conditions, experiments are performed with four magnetic spinel ferrites MFe₂O₄ (M = Co, Cu, Ni, and Zn) and two inorganic oxidants, i.e., hydrogen peroxide (HP) and potassium peroxymonosulfate (PMS). The reactions are performed using p‐nitrophenol as phenolic probe. CuFe₂O₄ and CoFe₂O₄ possessed excellent ability to activate HP and PMS, respectively, among all four synthesized catalysts. A noteworthy aspect of two oxidizing agents is that the concentration of PMS used during the reaction is four times less than HP. Further, the broad pH activity of PMS provides a significant advantage over HP. The optimal reaction conditions, when HP is the oxidant in the photo‐Fenton degradation, are 0.50 g L^?1 MFe₂O₄, pH 2.5, and 8.8 mM HP. Although PMS is active in a wide pH range (2–10), adequate reaction conditions are 0.50 g L^?1 MFe₂O₄, natural pH, and 2.2 mM PMS. The photo‐Fenton activity of ferrites is extended to the degradation of different nitro‐ and chloro‐analogs of phenol (2‐nitrophenol, 3‐nitrophenol, 4‐nitrophenol, 2,4‐dinitrophenol, 2,4,6‐trinitrophenol, 2‐chlorophenol, 3‐chlorophenol, 4‐chlorophenol, 2,4‐dichlorophenol) with only two ferrites (CuFe₂O₄ and CoFe₂O₄). A comparative study is performed with the two oxidants (HP and PMS) with positive results. Finally, stability and reusability of magnetic ferrites as catalysts are also studied to prove their use in phenolic solution treatment.     

不同pH处理对菹草(Potamogeton crispus L.)Cr6+毒害效应的影响

对Cr⁶⁺胁迫条件下不同pH处理对菹草无菌苗元素、光合色素、活性氧、丙二醛、抗氧化酶、脯氨酸(Pro)及多胺(PAs)含量的影响进行研究,以探讨不同pH处理影响水生植物Cr⁶⁺毒害效应的机制.结果表明:(1)偏酸性pH处理加剧菹草对铬的蓄积,而pH为7.0时Cr⁶⁺胁迫所造成的矿质元素失衡有所减弱;(2)Cr⁶⁺胁迫下pH为6.0~8.0的处理延缓了菹草的失绿症状,促进了光合色素的合成;(3)Cr⁶⁺胁迫下菹草超氧化物歧化酶、过氧化氢酶的活性在pH为6.0和7.0的处理组诱导程度最小;(4)Cr⁶⁺胁迫下pH为6.0和7.0处理的菹草Pro含量显著提高;(5)pH为4.0和5.0的处理使腐胺(Put)含量显著提高,而pH为6.0和7.0的处理则促进亚精胺(Spd)含量及游离态(Spd+Spm)/Put比值上升,精胺(Spm)含量总体趋势为随pH值升高而逐步上升,仅在pH为4.0和5.0的处理组中低于Cr⁶⁺胁迫对照组.因此,pH条件可影响菹草对铬及营养元素的积累,抗氧化酶、Pro、PAs代谢等生理生化过程,导致铬毒性效应差异.在pH为6.0~7.0的范围内,菹草能调节抗氧化酶系统,较有效地清除体内活性氧,提高机体中Pro、PAs含量及游离态(Spd+Spm)/Put比值,减轻膜系统脂质过氧化,维持机体内矿质元素平衡,致使毒性效应达到最小程度.     

镍添加对水鳖(Hydrocharis dubia)叶片镍和营养元素含量以及氧化胁迫和抗氧化系统的影响

采用营养液水培的方法,研究不同镍(Ni)添加浓度(0、0.05、0.10、0.15、0.20 mmol/L)对水鳖(Hydrocharis dubia)叶片中Ni元素积累、营养元素(Ca、Mg、K、Fe和Mn)含量、氧化胁迫和抗氧化系统的影响.结果显示:(1)叶片中Ni含量以浓度依赖的方式增加;(2)叶片中营养元素含量(Ca、Mg、K、Fe、Mn)也受影响,其中Ca、Mg含量随Ni浓度增加而显著上升;K含量随Ni浓度增加有所升高,但不显著;Mn含量虽在较大Ni浓度时有所下降,但处理组始终高于对照组;而Fe含量则随Ni浓度增加而下降;(3)Ni胁迫诱导了明显的氧化胁迫,主要表现为:O·-2产生速率以及过氧化氢和丙二醛含量显著升高,可溶性蛋白以及光合色素含量明显下降;(4)随着Ni浓度的升高,过氧化物酶活性逐渐升高,过氧化氢酶活性呈下降趋势,超氧化物歧化酶活性在Ni添加浓度为0.05 mmol/L时出现短暂升高随后下降;维生素E和黄酮含量随Ni浓度增加呈缓慢上升趋势;还原型谷胱甘肽未发生明显变化,非蛋白巯基和植物络合素含量均表现为先升后降的趋势;总抗氧化能力随Ni浓度升高先增强后减弱.由此可见,Ni添加引起水鳖叶片中Ni元素的累积和营养元素含量变化,同时产生明显的氧化胁迫,打破了抗氧化系统的平衡.     

Response Surface Approach for the Bisorption of Ag(I) by Macrofungus Pleurotus platypus

Response surface methodology (RSM) employing the three‐level Box–Behnken factorial design was used to optimize the biosorption of Ag(I) by the macrofungus Pleurotus platypus. The initial Ag(I) concentration (100–300 mg/L), pH (3.0–9.0), and biomass dosage (1.0–5.0 g/L) were chosen as the process variables for the optimization. A coefficient of determination (R²) value (0.99), model F value (234.18), and its low p‐value (F < 0.0001) along with the lower value of coefficient of variation (2.44%) indicated the fitness of response surface quadratic model during the present study. At the optimum pH (6.0), initial metal concentration (220 mg/L), and biomass dosage (3.0 g/L), the model predicted 46.7 mg/g Ag(I) uptake and an experimental 46.77 mg/g Ag(I) uptake by P. platypus was obtained. This is the first report on Ag(I) sorption by P. platypus using statistical experimental design employing RSM which may be helpful towards the treatment of industrial effluent containing silver.     

Sediment‐water Fluxes of Nutrients and Dissolved Organic Carbon in Extensive Sea Cucumber Culture Ponds

Sediment samples were collected from three seawater aquaculture ponds, and soil characteristics, sediment oxygen consumption (SOC), dissolved organic carbon (DOC) and nutrient fluxes were measured using chamber incubations at laboratory. The three ponds were each representing a specific monoculture or polyculture model of sea cucumber. Total organic carbon (TOC) and total nitrogen (TN) contents in the dry sediment ranged from 0.14 to 0.26% and 0.022 to 0.037%, respectively. Total phosphorus (TP) contents in the sediment were more spatially and temporally variable. SOC ranged from 15.29 to 45.86 mmol m^–2 d^–1 and showed significant differences among the three ponds (p < 0.05). TOC, total carbon (TC) contents, and SOC of the sediment in the pond polycultured with jellyfish increased with culture time, indicating that jellyfish farming enhanced the accumulation of organic matter in the sediments to some extent. Sediment showed net nitrate and ammonium uptake in most ponds and months, and significant differences were found among months (p < 0.05). Dissolved inorganic phosphate (DIP) was released from the sediments in all ponds with low flux rates. DOC was released from the sediment in all ponds and ranged from 0.67 to 1.74 g DOC m^–2 d^–1. The results suggested that non‐artificial‐feeding sea cucumber culture ponds could not only yield valuable seafood products, but also effectively remove nutrients from the aquaculture systems and consequently alleviate nutrient loadings of the nearby coast.     

Characterization of Estuarine and Fluvial Dissolved Organic Matter by Thermochemolysis using Tetramethylammonium Hydroxide

Selected samples of dissolved organic matter (DOM) isolated by ultrafiltration (UDOM) have been analyzed by thermochemolysis in the presence of tetramethylammonium hydroxide (TMAH). This technique cleaves ester and ether bonds of bio‐ and geological macromolecules and releases monomer subunits and methylates them in situ as their methyl ethers and methyl esters. Compared with conventional pyrolysis, TMAH thermochemolysis avoids decarboxylation of preexisting carboxylic moieties and produces aromatic acids as their methyl esters. Various phenolic derivatives, which might originate from incorporated lignin‐derived structures, from the highly aliphatic and resistant biopolymer cutan and also from proteinaceous materials, were identified among the products produced from UDOM upon thermochemolysis. The presence of lignin derivatives in UDOM indicates input of organic matter derived from terrestrial sources. Various aromatic acids, perhaps representing the final steps in the oxidation of the side‐chain during microbial oxidation of lignin, were released upon TMAH thermochemolysis, suggesting they are structural constituents of the UDOM. Different ratios of lignin‐derived materials, commonly determined using the CuO oxidation method, such as the Δ value, indicative of the amount of lignin present, the acid/aldehyde ratio (Ad/Al)_G, indicative of the extent of oxidative degradation of the lignin component, and the syringyl/guaiacyl (S/G) and p‐hydroxyphenyl/guaiacyl (P/G) ratios, indicative of the contribution for the different types of lignin, were determined.     

Amendment of Copper Toxicity in Alluvial Soil Using Iron: Effect on Growth and Yield of Triticum aestivum L.

Pot experiments were conducted in glasshouse under controlled conditions. The effect of copper in alluvial soil on the growth and yield of Triticum aestivum L. (wheat) was worked out. Copper was applied in soil at 5–100 mg L^?1, along with iron supplement. Inhibitory response of copper was significant (p < 0.05) confirmed by the plant growth parameters viz., plant height, fresh and dry weight, moisture content, pigment contents, protein, sugar contents followed by increased catalase and peroxidase activity in the harvest at 30, 60, and 90 days, of treatment, respectively. The plants grown on copper treated soil along with 5 mg L^?1 Cu and iron application showed significant effects (p < 0.05) regarding the increase in plant biomass, plant height (shoot only), pigment contents, protein, sugar contents, grain yield followed by decreased catalase and peroxidase activity in wheat after 30, 60, and 90 days of treatment, respectively. The accumulation of metal in plant tissues was found in order of Fe > Cu coupled by less translocation in grain as compared to the whole plant.     

Biomonitoring of Ni and V Contamination Using Oysters (Saccostrea cucullata) at Lengeh Port,Persian Gulf,Iran

Vanadium and nickel are two important indicators of oil pollution. Lengthy exposure to these elements causes serious harmful effects in human health, different harsh allergies being examples. The accumulation of two heavy metals (Ni and V) in sediment and the soft and hard tissues of Saccostrea cucullata were analyzed at three sampling sites along the coast of Lengeh Port, Persian Gulf. Results indicated at all the sampling sites; the Ni levels in soft tissues (STs) were higher than in the shells (SHs) and sediments, whereas the V levels were higher in the sediments. In addition, meaningful relationship (r = 0.65; p < 0.05) was observed across Ni levels in ST of S. cucullata and sediment, while for V concentrations a strong relationship (r = 0.83; p < 0.01) was found in SH of S. cucullata and sediment. This indicates that ST and SH of oyster can be considered as a biomonitoring agent for Ni and V levels, in coastal waters, respectively. The exposure of the consumer is compared directly to minimal risk level and provisional maximum tolerable daily intake. Result indicated that levels of Ni and V were within the safety limits for human consumption.     

Preconcentration by Coprecipitation of Copper and Nickel with Mo(VI)/Triazole Derivative System and Their Determinations by Flame Atomic Absorption Spectrometry in Food and Water Samples

A new separation and preconcentration technique based on coprecipitation of Cu(II) and Ni(II) ions by the aid of Mo(VI)/di‐tert‐butyl{methylenebis[5‐(chlorobenzyl)‐4H‐1,2,4‐triazol‐3,4‐diyl]}biscarbamate (BUMECTAC) precipitate has been established. The Mo(VI)/BUMECTAC precipitate was dissolved by concentrated HNO₃ and the solution was completed to 5.0 mL with distilled/deionized water. The levels of the analyte ions were determined by flame atomic absorption spectrometer. The effects of experimental conditions like HNO₃ concentration, amount of BUMECTAC and Mo(VI), sample volume, etc. and also the influences of some foreign ions were investigated in detail on the quantitative recoveries of analyte ions. The preconcentration factors were found to be 40 for Cu(II) and 100 for Ni(II) ions. The detection limits for Cu(II) and Ni(II) ions based on 3σ (N:10) were 0.43 and 0.70 µg L^?1, respectively. The relative standard deviations were found to be lower than 4.0% for both analyte ions. The accuracy of the method was checked by spiked/recovery tests and the analysis of two certified reference materials (Environment Canada TM‐25.3 and CRM‐SA‐C Sandy Soil C). The procedure was successfully applied to sea water and stream water as liquid samples and baby food as solid sample in order to determine the levels of Cu(II) and Ni(II) ions.     

Simultaneous and Sensitive HPLC Determination of Mono‐ and Disaccharides,Uronic Acids,and Amino Sugars after Derivatization by Reductive Amination

The reductive amination of low‐molecular‐weight saccharides, uronic acids, and amino sugars, followed by a separation of the derivates by means of ion‐pair chromatography or RP‐HPLC, offers an interesting alternative to HPAEC‐PAD for the environmental analysis of these compounds. Under this aspect various potential amination reagents, i.e., p‐amino‐benzoic acid (p‐AMBA), p‐AMBA propyl ester, 1‐aminopyrene, 2‐(2‐aminophenyl)indole, and 4‐aminoazobenzene, were tested with regard to the formation of derivates and to the chromatographic properties of the formed derivates. p‐AMBA, p‐AMBA propyl ester and 4‐aminoazobenzene proved to be especially suited, because they facilitate the amination of all carbohydrate reference components together with a complete separation and sensible detection (detection limits < 0.5 mg/L) of the derivates. Mainly the following elution sequence was ascertained: amino sugars (hexosamines) / disaccharide(s) / monosaccharides (hexoses) / hexuronic acid(s) / N‐acetyl‐D‐glucosamine. Detection limits down to 0.1 μmol/L were realized using p‐AMBA as reagent, facilitating the determination of the target compounds in landfill leachates and lysimeter percolates. Applying the p‐AMBA propyl ester for derivatization, chromatographic interferences with weakly retained derivates and the coelution of the reagent with its galactosamine derivate can be avoided, since the ester elutes after its derivates unlike p‐AMBA itself.     

Application of Mineral‐Based Amendments for Enhancing Phytostabilization in Lolium perenne L. Cultivation

An experimental investigation is conducted to explore the suitability of Lolium perenne L., diatomite, chalcedonite, dolomite, and limestone for the phytostabilization of Ni and Cu in contaminated soil. A controlled greenhouse study is conducted. The soil is enriched with rising dose of Cu and Ni, that is, (0, 150, 250, and 350 mg kg^?1) and (0, 150, 300, and 450 mg kg^?1), respectively. The phytostabilization potential of perennial ryegrass is evaluated using a bioaccumulation coefficient and translocation factor. Pseudo‐total and available metal content (0.01 M CaCl₂) in soils and bioaccumulated content in plants are defined in laboratory experiments using spectrophotometry experimental technique. L. perenne is adequate in phytostabilization aided programs, simultaneously, diatomite, chalcedonite, dolomite, and limestone used as modifiers are effective in reducing the accessibility and mobility of metals in Cu‐ and Ni‐polluted soils. The finding of the present study suggests that the studied element in the roots and above‐ground parts of L. perenne differs significantly upon applying mineral‐based modifications to the soil, synchronously the effect of increasing Cu and Ni levels. Application of dolomite and limestone to the soil cause the highest percentage of the above‐ground biomass. Diatomite along with limestone cause a significant boost of Cu and Ni absorption in the roots. Limestone causes an increase in the contents of K, Na, and Ca, as well as a reduction in P in the above‐ground parts of L. perenne. Limestone and chalcedonite leads to the highest decrease in available Cu and Ni.     

Investigation of Arsenotrophic Microbiome in Arsenic‐Affected Bangladesh Groundwater

Arsenotrophic bacteria contribute to the nutrient cycling in arsenic (As) affected groundwater. This study employed a culture‐independent and ‐dependent investigation of arsenotrophic microbiomes in As affected groundwater samples collected from Madhabpur, Sonatengra, and Union Porishod in Singair Upazila, Manikganj, Bangladesh. Total As contents, detected by Atomic Absorption Spectrophotometry (AAS) of the samples, were 47 µg/L (Madhabpur, SNGW‐1), 53 µg/L (Sonatengra, SNGW‐2), and 12 µg/L (Union porishod, SNGW‐3), whereas the control well (SNGW‐4; depths >150 m) showed As content of 6 µg/L. Denaturing Gradient Gel Electrophoresis (DGGE) analysis of the amplified 16S rRNA gene from As‐affected groundwater samples revealed the dominance of aerobic bacteria Pseudomonas within heterogeneous bacterial populations. DGGE of heterotrophic enrichments supplemented with arsenite [As (III)] for 4 weeks showed the dominance of Chryseobacterium, Flavobacterium, and Aquabacterium, whereas the dominant genera in that of autotrophic enrichments were Aeromonas, Acinetobacter, and Pseudomonas. Cultured bacteria retrieved from both autotrophic and heterotrophic enrichments were distinguished into nine genotypes belonging to Chryseobacterium, Acinetobacter, Escherichia, Pseudomonas, Stenotrophomonas, Janibacter, Staphylococcus, and Bacillus. They exhibited varying range of As(III) tolerance from 4 to 27 mM. As(III) transformation potential was confirmed within the isolates with oxidation rate as high as 0.143 mM/h for Pseudomonas sp. Sn 28. The arsenotrophic microbiome specifies their potential role in groundwater As‐cycling and their genetic information provide the scientific basis for As‐bioremediation.     

Equilibrium,Kinetic, and Thermodynamic Studies on the Adsorption of Triclosan onto Multi‐Walled Carbon Nanotubes

The increased accumulation of toxic pharmaceuticals and personal care products in the environment is a concern of worldwide relevance. Efficient technologies are needed to mitigate the level of such chemicals in natural waters. The suitability of multi‐walled carbon nanotubes (MWCNTs) to remove aqueous triclosan (a widely used anti‐microbial agent) was investigated in the present study. Tested operational parameters included the pH (3.0–11.0) value and the ionic strength (10^?3, 10^?2, and 10^?1 M). Kinetic and thermodynamic studies were conducted at different initial concentrations (4, 8, and 10 mg/L) and temperatures (288, 298, and 308 K). Results showed higher triclosan adsorption at pH 3.0 (157.7 mg/g) than at pH 11.0 (103.9 mg/g). With an increase of ionic strength from 10^?3 to 10^?2 M, the adsorption capacity increased from 136.1 to 153.1 mg/g and from 80.8 to 105.8 mg/g at pH 3.0 and 10.0, respectively, while further increase of ionic strength to 10^?1 M slightly reduced the triclosan adsorption to 149.9 and 94.7 mg/g due to the aggregation of MWCNTs. The Polanyi–Manes model (PMM) provided a best fitting of adsorption isotherms to the experimental data, and the kinetic process was well described by the pseudo second‐order kinetic model. The calculated thermodynamic parameters (ΔH⁰ = ?88.08 kJ/mol, ΔS⁰ = ?173.38 J/mol K) suggested that the adsorption of triclosan is spontaneous and exothermic in nature. The findings of the present work have significant implications for the removal of triclosan from aqueous solution with MWCNTs.     

The Potential of Eleocharis acicularis for Phytoremediation: Case Study at an Abandoned Mine Site

Phytoremediation, a plant‐based and cost‐effective technology for the cleanup of contaminated soil and water, is receiving increasing attention. In this study, the aquatic macrophyte Eleocharis acicularis was examined for its ability to take up multiple heavy metals and its potential application for phytoremediation at an abandoned mining area in Hokkaido, Japan. Elemental concentrations were measured in samples of E. acicularis, water, and soil collected from areas of mine tailing and drainage. The results reveal that Pb, Fe, Cr, Cu, Ni, and Mn accumulation in the plants increased over the course of the experiment, exceeding their initial concentrations by factors of 930, 430, 60, 25, 10, and 6, respectively. The highest concentrations of Fe, Pb, Zn, Mn, Cr, Cu, and Ni within the plants were 59500, 1120, 964, 388, 265, 235, and 47.4 mg/kg dry wt., respectively, for plants growing in mine drainage after 11 months of the experiment. These results indicate that E. acicularis is a hyperaccumulator of Pb. We also found high Si concentrations in E. acicularis (2.08%). It is likely that heavy metals exist in opal‐A within cells of the plant. The bioconcentration factors (BCF: ratio of metal concentration in the plant shoots to that in the soil) obtained for Cr, Cu, Zn, Ni, Mn, and Pb were 3.27, 1.65, 1.29, 1.26, 1.11, and 0.82, respectively. The existence of heavy metals as sulphides is thought to have restricted the metal‐uptake efficiency of E. acicularis at the mine site. The results of this study indicate that E. acicularis shows great potential in the phytoremediation of mine tailing and drainage rich in heavy metals.     

Treatment of Domestic Sewage in an Anaerobic–Aerobic Fixed‐bed Reactor with Recirculation of the Liquid Phase

This study reports the performance of a combined anaerobic–aerobic packed‐bed reactor that can be used to treat domestic sewage. Initially, a bench‐scale reactor was operated in three experimental phases. In the first phase, the anaerobic reactor was operated with an average organic matter removal efficiency of 77% for a hydraulic retention time (HRT) of 10 h. In the second phase, the reactor was operated with an anaerobic stage followed by an aerobic zone, resulting in a mean value of 91% efficiency. In the third and final phase, the anaerobic–aerobic reactor was operated with recirculation of the effluent of the reactor through the anaerobic zone. The system yielded mean total nitrogen removal percentages of 65 and 75% for recycle ratios (r) of 0.5 and 1.5, respectively, and the chemical oxygen demand (COD) removal efficiencies were higher than 90%. When the pilot‐scale reactor was operated with an HRT of 12 h and r values of 1.5 and 3.0, its performance was similar to that observed in the bench‐scale unit (92% COD removal for r = 3.0). However, the nitrogen removal was lower (55% N removal for r = 3.0) due to problems with the hydrodynamics in the aerobic zone. The anaerobic–aerobic fixed‐bed reactor with recirculation of the liquid phase allows for concomitant carbon and nitrogen removal without adding an exogenous source of electron donors and without requiring any additional alkalinity supplementation.     

Preparation,Characterization of a Novel Chelating Resin Functionalized with o‐Hydroxybenzamide and Its Application for Preconcentration of Trace Metal Ions

A stable extractor of metal ions was synthesized through azo linking of o‐hydroxybenzamide (HBAM) with Amberlite XAD‐4 (AXAD‐4) and was characterized by elemental analyses, IR spectral, and thermal studies. Its water regain value and hydrogen ion capacity were found to be 12.93 and 7.68 mmol g^?1, respectively. The optimum pH range (with the half‐loading time [min], t_1/2) for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were 2.0–4.0 (5.5), 2.0–4.0 (7.0), 2.0–4.0 (8.0), 4.0–6.0 (9.0), 4.0–6.0 (12.0), and 2.0–4.0 (15.0), respectively. Comparison of breakthrough and overall capacities of the metals ascertains the high degree of column utilization (>70%). The overall sorption capacities for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were found to be 0.29, 0.22, 0.20, 0.16, 0.13, and 0.11 mmol g^?1 with the corresponding preconcentration factor of 400, 380, 380, 360, 320, and 320, respectively. The limit of preconcentration was in the range of 5.0–6.3 ng mL^?1. The detection limit for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) were found to be 0.39, 0.49, 0.42, 0.59, 0.71, and 1.10 ng mL^?1, respectively. The AXAD‐4‐HBAM has been successfully applied for the analysis of natural water, multivitamin formulation, infant milk substitute, hydrogenated oil, urine, and fish.     

Coprecipitation with Cu(II)‐4‐(2‐Pyridylazo)‐resorcinol for Separation and Preconcentration of Fe(III) and Ni(II) in Water and Food Samples

The coprecipitation method is widely used for the preconcentration of trace metal ions prior to their determination by flame atomic absorption spectrometry (FAAS). A simple and sensitive method based on coprecipitation of Fe(III) and Ni(II) ions with Cu(II)‐4‐(2‐pyridylazo)‐resorcinol was developed. The analytical parameters including pH, amount of copper (II), amount of reagent, sample volume, etc., were examined. It was found that the metal ions studied were quantitatively coprecipitated in the pH range of 5.0–6.5. The detection limits (DL) (n = 10, 3s/b) were found to be 0.68 µg L^?1 for Fe(III) and 0.43 µg L^?1 for Ni(II) and the relative standard deviations (RSD) were ≤4.0%. The proposed method was validated by the analysis of three certified reference materials (TMDA 54.4 fortified lake water, SRM 1568a rice flour, and GBW07605 tea) and recovery tests. The method was successfully applied to sea water, lake water, and various food samples.     

Soil C and N response to changes in winter precipitation in a subalpine forest ecosystem,NW Italy

Among the potential effects of climate change on subalpine forest ecosystems during the winter season, the shift in snowline towards higher altitudes and the increase in frequency of rain events on the snowpack are of particular interest. Here, we present the results of a 2‐year field experiment conducted in a forest stand (Larix decidua) in NW Italy at 2020 m a.s.l. From 2009 to 2011, we monitored soil physical characteristics (temperature and moisture), and soil and soil solution chemistry, in particular carbon (C) and nitrogen (N) forms and their change in time, as affected by simulated late snowpack accumulation and rain on snow events. Late snowpack accumulation determined a stronger effect on soil thermal and moisture regimes than rain on snow events. Also soil chemistry was significantly affected by late snowfall simulation. Although microbial biomass C and N were not reduced by soil freezing, soil contents of the more labile dissolved organic carbon and inorganic N increased when the soil was affected by mild/hard freezing. Variations in the soil solution were shifted with respect to those observed in soil, with an increase in N‐NO₃^? concentrations occurring during spring and summer. This study highlights the potential N loss in subalpine soils under changing environmental conditions driven by a changing climate. Copyright © 2013 John Wiley & Sons, Ltd.     

太湖流域滆湖底泥重金属赋存特征及其生物有效性

为了探讨太湖流域滆湖底泥重金属(Cd、Cr、Cu、Zn、Ni和Pb)的赋存特征及其生物有效性,对底泥重金属总量、形态以及生物富集量进行了分析.结果表明,6种重金属含量的空间分布表现为北部湖区最高,其次为南部湖区,中部湖区最低,重金属Ni、Cu、Zn和Pb含量显著高于沉积物背景值,分别是背景值的4.77、3.89、2.96和2.76倍,重金属总量与沉积物中的黏土成分含量具有显著相关性.采用三级四部提取法对重金属形态进行分析表明,6种重金属的生物有效态(弱酸结合态、可还原态和可氧化态之和)含量顺序为CdCuZnPbNiCr,其中Cd、Cu、Zn和Pb的生物有效态含量分别占总量的84.15%、78.47%、76.50%和64.29%.Cu和Zn在铜锈环棱螺中富集含量要显著高于其他金属元素.相关性分析表明,6种重金属中仅Cr和Pb的生物富集量与有效态含量具有显著相关性,这表明,重金属在生物体内的富集不仅与有效态含量有关,还与底泥重金属总量有关.因此,评价滆湖重金属的生态风险时需要综合考虑重金属的总量及生物有效态含量.