Effect of pH and coexisting anions on removal of phosphate from aqueous solutions by inorganic-based mesostructures

This study investigated the effect of pH and the presence of coexisting (competitive) anions on the removal of phosphate by titanium mesostructures synthesized using do- or hexadecyltrimethylammonium bromide. To address these research objectives, experiments were conducted (1) under controlled initial pH values (2 to 10); and (2) through injection of nitrate, fluoride, chloride, or sulfate anions into a phosphate solution. Based on the experimental results, an initial of pH of 2 was found to be optimal for use of titanium mesostructures. The presence of fluoride anions in solution significantly decreased the removal efficiency of phosphate removal (3.56% at 3.95 mg/g). However, the addition of nitrate, chloride, and sulfate anions did not affect phosphate removal.     

老港填埋场新鲜渗滤液性质研究

用系列滤膜对老港填埋场2003年3月份新鲜渗滤液进行了梯度分离．并研究了其CODcr、氨氮、TOC、IC、TC、TS、FS、电导率、pH、色度,浊度的变化趋势与不同孔径膜之间的关系。结果表明,随着膜孔径的减小,CODcr、氨氮、TOC、IC、TC、TS、FS、色度、浊度等都有不同程度的降低,但降低不大,说明可溶性部分物质对新鲜渗滤液的污染性贡献最大;电导率、pH则先增大后减小。     

Measurements of PM10 and PM2.5 in urban area of Nanjing,China and the assessment of pulmonary deposition of particle mass

Measurement of PM10 and PM2.5 was carried out at six sites of Nanjing, China in the period of February-May 2001. The pH and conductivity of water-soluble matter of PM10 and PM2.5 were determined, and the samples were analyzed for total carbon (TC), organic carbon (OC) and inorganic carbon (IC) of the water-soluble fraction. The distribution of aerosol mass concentration in size was also measured at one site SB by a nine-stage impactor followed to assess the pulmonary deposition of particles in different tracts of the human respiratory system. Compared with National Ambient Air Quality Standard (NAAQS) of the USA, the level of PM10 and PM2.5 in Nanjing was much higher. Especially for site SY, the average particle mass concentrations (774.5 micrograms/m3 for PM10 and 481.4 micrograms/m3 for PM2.5) were more than five times the NAAQS standard. At site SB aerosol mass distribution in size had shown the similar characteristics with accumulation (Dp < 1 micron) and coarse (Dp > 1 micron) modes. More than 70% of total suspended particles is of a size that they are deposited in the respiratory tract below trachea, whereas about 22% of the mass is respirable and will reach the alveoli. Water-soluble fractions of PM10 and PM2.5 in Nanjing are acidic, and the pH of PM2.5 is lower than that of PM10. OC makes up the majority of TC and accounts for 3-14% of mass concentration of PM10 and/or PM2.5, while IC only accounts for 0.1-0.5% of PM10 and/or PM2.5 mass.     

Chemical composition of fresh snowfalls at Palmer Station,Antarctica

A first time investigation was performed to establish a chemical baseline for snowfall at Palmer Station Antarctica (64°46′S, 64°05′W) since there was no such record. A chemical baseline for snow could be use to validate climate change studies based on ice core analyses. The snow samples contained (from high to low mass concentration) total organic carbon, chloride, inorganic carbon, sodium, sulfate, magnesium, calcium, potassium, fluoride, ammonium, and nitrate, excluding hydrogen and hydroxide. The pH of these samples ranged between 4.0–6.2. The relatively low nitrate and relatively high sulfate concentrations found in our samples are consistent with the results of other studies for this region of Antarctica. The ions and pH do not appear to favor a particular wind direction during this period. The total deposition of sulfate and flouride via snowfall between 10 January and 10 February is conservatively estimated to be 4.78 and 1.3 kg km^-2, respectively.     

Process-based reactive transport modeling of a permeable reactive barrier for the treatment of mine drainage

Reactive transport modeling of a permeable reactive barrier for the treatment of mine drainage was used to integrate a comprehensive data set including pore water chemistry and solid phase data from several sampling events over a >3-year time period. The simulations consider the reduction of sulfate by the organic carbon-based treatment material and the removal of sulfate and iron by precipitation of reduced mineral phases including iron monosulfides and siderite. Additional parameters constraining the model include dissolved H2S, alkalinity and pH, as well as a suite of solid phase S-fractions identified by extractions. Influences of spatial heterogeneity necessitated the use of a 2-dimensional modeling approach. Simulating observed seasonal fluctuations and long-term changes in barrier reactivity required the use of temperature dependent rate coefficients and a multimodal Monod-type rate expression accounting for the variable reactivity of different organic carbon fractions. Simulated dissolved concentrations of SO4, Fe, H2S, alkalinity and pH, as well as solid phase accumulations of reduced sulfur phases generally compare well to observed trends over 23 months. Spatial variations, seasonal fluctuations and the time-dependent decline in reactivity were also captured. The modeling results generally confirm, and further strengthen, the existing conceptual model for the site. Overall sulfate reduction and S-accumulation rates are constrained with confidence within a factor of 1.5.     

Sulfate,chloride and fluoride retention in Andosols exposed to volcanic acid emissions

The continuous emissions of SO(2), HCl and HF by Masaya volcano, Nicaragua, represent a substantial source of atmospheric S-, Cl- and F-containing acid inputs for local ecosystems. We report on the effects of such acid depositions on the sulfate, chloride and fluoride contents in soils (0-40 cm) from two distinct transects located downwind from the volcano. The first transect corresponds to relatively undifferentiated Vitric Andosols, and the second transect to more weathered Eutric Andosols. These soils are exposed to various rates of volcanogenic acid addition, with the Vitric sites being generally more affected. Prolonged acid inputs have led to a general pH decrease and reduced exchangeable base cation concentrations in the Andosols. The concentrations of 0.5 M NH(4)F- and 0.016 M KH(2)PO(4)-extractable sulfate (NH(4)F-S and KH(2)PO(4)-S, respectively) indicate that volcanic S addition has increased the inorganic sulfate content of the Vitric and Eutric soils at all depths. In this process, the rate of sulfate accumulation is also dependent on soil allophane contents. For all soils, NH(4)F extracted systematically more (up to 40 times) sulfate than KH(2)PO(4). This difference suggests sulfate incorporation into an aluminum hydroxy sulfate phase, whose contribution to total inorganic sulfate in the Vitric and Eutric Andosols is estimated from approximately 34 to 95% and approximately 65 to 98%, respectively. The distribution of KH(2)PO(4)-extractable chloride in the Vitric and Eutric Andosols exposed to volcanic Cl inputs reveals that added chloride readily migrates through the soil profiles. In contrast, reaction of fluoride with Al and Fe oxyhydroxides and allophanes is an important sink mechanism in the Masaya Andosols exposed to airborne volcanic F. Fluoride dominates the anion distribution in all soil horizons, although F is the least concentrated element in the volcanic emissions and depositions. The soil anion distribution reflects preferential retention of fluoride over sulfate and chloride, and of sulfate over chloride. The primary acidifying agent of the Andosols subject to the volcanic acid inputs is HCl.     

Fluoride removal performance of a novel Fe-Al-Ce trimetal oxide adsorbent

A trimetal oxide was developed as a fluoride adsorbent by coprecipitation of Fe(II), Al(III) and Ce(IV) salt solutions with a molar ratio of 1:4:1 under alkaline condition. The material retained amorphous structure and maintained relatively stable fluoride adsorption performance at calcination temperatures lower than 600 degrees C. The optimum pH range for fluoride adsorption was 6.0-6.5 and the adsorbent also showed high defluoridation ability around pH 5.5-7.0, which is preferable for actual application. A high fluoride adsorption capacity of 178 mg g(-1) was acquired under an equilibrium fluoride concentration of 84.5 mg l(-1), adsorbent dose of 150 mg l(-1) and pH 7.0. The adsorption isotherm could be better described by the two-site Langmuir model than the one-site model, suggesting the existence of two types of active sites on the adsorbent surface. Coexistence of high concentrations of phosphate or arsenate only led to partial inhibition of fluoride adsorption, which further suggests the existence of heterogeneous adsorption sites. Sulfate and chloride did not affect fluoride adsorption, and nitrate influenced it only when the concentration of NO(3)(-)-N exceeded 50 mg l(-1). A high desorption efficiency of 97% was achieved by treating fluoride loaded Fe-Al-Ce oxide with NaOH solution at pH 12.2. A column experiment using the adsorbent fabricated into 1mm pellets was performed at an initial fluoride concentration of 5.5 mg l(-1), space velocity of 5h(-1) and pH of 5.8, and 2240 bed volumes were treated with the effluent fluoride under 1.0 mg l(-1).     

碱式硫酸铝溶液吸收二氧化硫

为了探讨碱式硫酸铝对二氧化硫的吸收效果，对所需试剂硫酸铝和碳酸钙的适宜比例（碱度），以及碱式硫酸铝能稳定存在的铝量范围等进行了研究，测定了不同铝量和碱度的碱式硫酸铝对二氧化硫的吸收量以及pH值，并分析每种吸收液的饱和吸收量，最后将其与乙二胺/磷酸溶液的吸收情况进行对比。结果表明，碱度为40%时，铝量要保持在70 g/L以下才能在加热时不产生沉淀，吸收过程pH由4.5左右一直下降到2.0左右保持稳定，饱和吸收时间控制在140~160 min为宜，较为理想的方案是铝量32 g/L，碱度35%。     

Comparative effectiveness of mixed organic substrates to mushroom compost for treatment of mine drainage in passive bioreactors

Bioreactors are one possible best sustainable technology to address the mine-impacted water problems. Several prospective substrates (mushroom compost, cow manure, sawdust, wood chips, and cut rice straw) were characterized for their ability to serve as a source of food and energy for sulfate-reducing bacteria. Twenty bench-scale batch bioreactors were then designed and set up to investigate relative effectiveness of various mixtures of substrates to that of mushroom compost, the most commonly used substrate in field bioreactors, for treating mine drainage with acidic (pH 3) and moderate pH (pH 6). Overall, reactive mixtures showed satisfactory performances in generating alkalinity, reducing sulfate and removing metals (Al>Fe>Mn) (up to 100%) at both pH conditions, for all substrates. The mixture of sawdust and cow manure was found as the most effective whereas the mixture containing 40% cut rice straw gave limited efficiency, suggesting organic carbon released from this substrate is not readily available for biodegradation under anaerobic conditions. The mushroom compost-based bioreactors released significant amount of sulfate, which may raise a more concern upon the start-up of field-scale bioreactors. The correlation between the extent of sulfate reduction and dissolved organic carbon/SO(4)(2-) ratio was weak and this indicates that the type of dissolved organic carbon plays a more important role in sulfate reduction than the absolute concentration and that the ratio is not sensitive enough to properly describe the relative effectiveness of substrate mixtures.     

Dioxin screening in fish product by pattern recognition of biomarkers

Two alternative, cost- and time-effective dioxin screening methods relying on two categories of potential lipid biomarkers were investigated. A dioxin range varying from 1.1 to 47.1 pg PCDD/F TEQ-WHO/g lipid using 64 fish meal samples was used for model calibration. The methods were based on multivariate models using either (1) fatty acid composition monitored by GC-FID or (2) fluorescence landscape signals analysed using the PARAFAC model and in both cases predicting dioxin content as pgPCDD/F TEQ-WHO/g lipid. In both cases, Partial Least Squares (PLS) regression was performed for predicting the dioxin content of a sample. The GC-FID data analyses was based on automatic peak alignment and integration, enabling extraction of the area of 140 peaks from the gas chromatograms, as opposed to the 31 fatty acids usually considered for fish oil characterisation. In addition to classic PLS employing the whole dataset for calibration, a two-step local PLS modeling approach was performed based upon an initial selection of k number of calibration samples providing the best match to the prediction sample using a so-called k Nearest Neighbors (kNN) approach, then followed by PLS calibration on these kNN selected samples for dioxin prediction. Fluorescence spectroscopy offers a promising non-invasive and ultra-rapid technique, with less than two minutes analysis time. However, fluorescence spectroscopy using the pattern recognition "kNN-PLS" yielded a correlation of 0.76 (r2) and a high root mean square error of prediction of 11.4 pg PCDD/F TEQ-WHO/g lipid. The predictions were improved when the PLS calibration was performed on all the sample with a root mean square error of prediction of 7.0 pg PCDD/F TEQ-WHO/g lipid. Unfortunately, these results failed to demonstrate the potential of fluorophore monitoring as a screening method. In contrast, the overall best screening performance was obtained with the fatty acid profile, when the kNN-PLS combination employed for pattern recognition (kNN) all the areas of the 140 detected peaks and the PLS regression used the areas of 46 selected peaks. This "kNN-PLS" prediction with three latent variables and based upon the 12 nearest neighbors selected out of the 64 x 2 fatty acid profiles (duplicate analyses), yielded a correlation of 0.85 (r2) and a root mean square error of prediction of 2.1 pg PCDD/F TEQ-WHO/g lipid and resulted in a total analysis time of one and half hour per sample.     

Decomposition of phorate in aqueous solution by ozonation

Phorate (O,O-diethyl S-ethylthiomethyl phosphorodithioate) dissolved in aqueous solution was almost completely decomposed by ozonation to form various species within 10 minutes of reaction time for the experimental conditions examined in this research. The generation rate of sulfate was found to be fairly independent of solution pH value. However, the formation of phosphate and carbonate was more favorable for alkaline solutions where hydroxyl free radical is the primary oxidative species. The reaction rates increased with initial gaseous ozone concentrations, indicating the reaction was mass transfer-controlled within the experimental range of this research. Combining the analytical results by various instruments, including gas chromatograph equipped with an electron ionization detector (GC-EID), high performance liquid chromatography (HPLC), ion chromatography (IC), and total organic carbon (TOC), the temporal sequence of phorate ozonation was proposed in this study. The oxidation of sulfur atoms on the phosphorus-sulfur double bond or carbon-sulfur-carbon bond by ozonation was found to occur at first to form sulfate and various intermediates.     

Modelling of dissolved oxygen content using artificial neural networks: Danube River, North Serbia, case study

The aims of this study are to create an artificial neural network (ANN) model using non-specific water quality parameters and to examine the accuracy of three different ANN architectures: General Regression Neural Network (GRNN), Backpropagation Neural Network (BPNN) and Recurrent Neural Network (RNN), for prediction of dissolved oxygen (DO) concentration in the Danube River. The neural network model has been developed using measured data collected from the Bezdan monitoring station on the Danube River. The input variables used for the ANN model are water flow, temperature, pH and electrical conductivity. The model was trained and validated using available data from 2004 to 2008 and tested using the data from 2009. The order of performance for the created architectures based on their comparison with the test data is RNN > GRNN > BPNN. The ANN results are compared with multiple linear regression (MLR) model using multiple statistical indicators. The comparison of the RNN model with the MLR model indicates that the RNN model performs much better, since all predictions of the RNN model for the test data were within the error of less than ±10 %. In case of the MLR, only 55 % of predictions were within the error of less than ±10 %. The developed RNN model can be used as a tool for the prediction of DO in river waters.     

氯化镁复配硫酸铝混凝性能及絮体特性

在研究氢氧化镁混凝特性的基础上,复配氯化镁和硫酸铝作为混凝剂,以高岭土配水水样为研究对象,运用iPDA在线监测技术对混凝过程絮体形成进行监测,探讨了单独使用氯化镁和硫酸铝以及二者复配使用的混凝效果和絮体特性,确定复配使用的各种条件。结果表明,对于浊度20 NTU,pH 11.5的高岭土配水水样,氯化镁、硫酸铝最佳投加量分别为7.2 mg/L(Mg2+计)和3 mg/L(Al3+计);硫酸铝跟氯化镁复配使用时,先投加硫酸铝,间隔30 s后投加氯化镁,混凝效果较好;在镁离子最佳投加量7.2 mg/L时,铝和镁最佳质量比在1∶3~1∶2之间;镁铝复配时其FI值明显大于单独作用时,即絮体尺寸大小:二者复配硫酸铝氯化镁,而且复配条件下Zeta电位值在零电势左右浮动,浮动范围小,更利于聚集沉淀;镁铝复配时发生了协同效应,弥补了单独使用氯化镁混凝过程的不足。     

电增强载铝活性炭纤维吸附除氟的效果与影响因素

以含氟地下水为研究对象,采用自制电促吸附除氟反应器,开展电增强载铝活性炭纤维吸附除氟的动态实验,研究了不同电压、极板间距、地下水碱度和流速对吸附除氟效果的影响。实验结果表明,在负载炭纤维毡的电极一端加正电,可以提高除氟效果。当电压为1.6 V时除氟效果较好,单位面积炭毡处理达标水量为56.7 L/m2;极板间距设置为4mm时电吸附反应器除氟效果最佳;通过调节pH改变地下水碱度,当地下水pH调节为5.5时,电吸附反应器除氟效果较未调节前提高50%;当采用3对电极板,流速为1.88 m/h时,达到最高表面处理负荷2 073.6 L/(m2.d);探究了反应器的反洗再生方式,并连续进行了吸附再生的动态实验;穿透的反应器以Al2(SO4)3溶液为再生液并采用反向加电1.6 V的方式,可以达到较好的再生效果,实现连续动态运行。     

A predictive model for copper partitioning to suspended particulate matter in river waters

A chemical equilibrium-based predictive model expressing Cu partitioning as a function of aqueous and solid phase characteristics was developed. The model takes into account only the most important factors that govern Cu partitioning, and therefore results in a relatively simple formulation. It assumes particulate organic carbon (POC) and dissolved organic carbon (DOC) binding sites play the most important role in solid and aqueous phases. The model formulation assumed one-surface site and two dissolved organic matter (DOM) sites, and included the "solids effect". Proton effects were considered for both the particle surface sites and the DOM. The model was calibrated with data for samples collected from the Susquehanna River, and validated with White Clay Creek and Delaware River samples. Copper partitioning in natural water systems with different pH, and concentrations of alkalinity, DOC, POC, total suspended solids (TSS), and total copper was predicted reasonably well.     

Hardness corrections for copper are inappropriate for protecting sensitive freshwater biota

Toxicity testing using a freshwater alga (Chlorella sp.), a bacterium (Erwinnia sp.) and a cladoceran (Ceriodaphnia cf. dubia) exposed to copper in synthetic and natural freshwaters of varying hardness (44-375 mg CaCO3/l), with constant alkalinity, pH and dissolved organic carbon concentration, demonstrated negligible hardness effects in the pH range 6.1-7.8. Therefore, the use of a generic hardness-correction algorithm, developed as part of national water quality guidelines for protecting freshwater biota, is not recommended for assessing the toxicity of copper to these, and other, sensitive freshwater species. Use of the algorithm for these sensitive species will be underprotective because the calculated concentrations of copper in water that cause a toxic effect will be higher.     

Simultaneous determination of three herbicides by differential pulse voltammetry and chemometrics

A novel differential pulse voltammetry method (DPV) was researched and developed for the simultaneous determination of Pendimethalin, Dinoseb and sodium 5-nitroguaiacolate (5NG) with the aid of chemometrics. The voltammograms of these three compounds overlapped significantly, and to facilitate the simultaneous determination of the three analytes, chemometrics methods were applied. These included classical least squares (CLS), principal component regression (PCR), partial least squares (PLS) and radial basis function-artificial neural networks (RBF-ANN). A separately prepared verification data set was used to confirm the calibrations, which were built from the original and first derivative data matrices of the voltammograms. On the basis relative prediction errors and recoveries of the analytes, the RBF-ANN and the DPLS (D – first derivative spectra) models performed best and are particularly recommended for application. The DPLS calibration model was applied satisfactorily for the prediction of the three analytes from market vegetables and lake water samples.     

Simultaneous determination of three herbicides by differential pulse voltammetry and chemometrics

A novel differential pulse voltammetry method (DPV) was researched and developed for the simultaneous determination of Pendimethalin, Dinoseb and sodium 5-nitroguaiacolate (5NG) with the aid of chemometrics. The voltammograms of these three compounds overlapped significantly, and to facilitate the simultaneous determination of the three analytes, chemometrics methods were applied. These included classical least squares (CLS), principal component regression (PCR), partial least squares (PLS) and radial basis function-artificial neural networks (RBF-ANN). A separately prepared verification data set was used to confirm the calibrations, which were built from the original and first derivative data matrices of the voltammograms. On the basis relative prediction errors and recoveries of the analytes, the RBF-ANN and the DPLS (D - first derivative spectra) models performed best and are particularly recommended for application. The DPLS calibration model was applied satisfactorily for the prediction of the three analytes from market vegetables and lake water samples.     

Stabilization of FGD gypsum for its disposal in landfills using amorphous aluminium oxide as a fluoride retention additive

The applicability of amorphous aluminium oxide as a fluoride retention additive to flue gas desulphurisation (FGD) gypsum was studied as a way of stabilizing this by-product for its disposal in landfills. Using a batch method the sorption behaviour of amorphous aluminium oxide was evaluated at the pH (about 6.5) and background electrolyte conditions (high chloride and sulphate concentrations) found in FGD gypsum leachates. It was found that fluoride sorption on amorphous aluminium oxide was a very fast process with equilibrium attained within the first half an hour of interaction. The sorption process was well described by the Langmuir model, offering a maximum fluoride sorption capacity of 61.7 mg g(-1). Fluoride sorption was unaffected by chloride co-existing ions, while slightly decreased (about 20%) by competing sulphate ions. The use of amorphous aluminium oxide in the stabilization of FGD gypsum proved to greatly decreased its fluoride leachable content (in the range 5-75% for amorphous aluminium oxide doses of 0.1-2%, as determined by the European standard EN 12457-4 [EN-12457-4 Characterization of waste-leaching-compliance test for leaching of granular waste materials and sludges-Part 4: one stage batch test at a liquid to solid ratio of 10 l/kg for materials with particle size below 10mm (without or with size reduction)]), assuring the characterization of this by-product as a waste acceptable at landfills of non-hazardous wastes according to the Council Decision 2003/33/EC [Council Decision 2003/33/EC of 19 December 2002. Establishing criteria and procedures for the acceptance of waste at landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC] on landfill of wastes. Furthermore, as derived from column leaching studies, the proposed stabilization system proved to be highly effective in simulated conditions of disposal, displaying a fluoride leaching reduction value about 81% for an amorphous aluminium oxide added amount of 2%.