聚合硅酸钛铝复合絮凝剂的结构及性能

为了克服有机絮凝剂的二次投加及有毒性的缺点,以硅酸钠、硫酸钛、硫酸铝为原料,制备了聚合硅酸钛铝(PTAS)无机高分子复合絮凝剂处理模拟江水。结果表明,在n(Ti+Al)∶n(Si)=1∶3,n(Ti)∶n(Al)=1∶5,模拟江水pH值为5～9.3,絮凝剂投加量为0.3 mmol/L(以金属离子计)时,PTAS对模拟江水的混凝效果最好,除浊率达到92.5%以上。此外,通过X-射线衍射说明聚硅酸与硫酸铝、硫酸钛不是单纯的原料复合;红外吸收光谱显示钛、铝离子及其水解聚合产物可与共存的聚硅酸生成Si—O—Al键和Ti—O—Si键;激光粒度分析表明PTAS在聚合过程中粒度并没有明显变化,但均比聚硅酸粒径大。     

The significance of water ionic strength on aluminium toxicity in brown trout (Salmo trutta L.)

The toxicity of aluminium to fish is related to interactions between aluminium and the gill surface. We investigated the possible effect of water ionic strength on this interaction. The mortality of brown trout (Salmo trutta L.) exposed to three different degrees of Al polymerisation was compared in water with increased ionic strength (mean 7.31 x 10(-4) M) after additions of the base cations Ca2+, Mg2+, Na+ or K+, and in water with no such addition (mean ionic strength 5.58 x 10(-4) M). Only a very slight ameliorating effect of increased ionic strength was observed, while the degree of Al polymerisation was of major importance in fish mortality. In addition, it was observed that smaller fish survived the Al exposures for a longer time than larger fish. We hypothesise that this is because larger fish are more susceptible to hypoxia than smaller fish.     

The chemical species distribution and transformation of polyaluminum silicate chloride coagulant

The chemical species distributions of polyaluminum silicate chloride (PASC) and polyaluminum chloride (PACl) determined by Al-Ferron complexation timed spectrophotometric and 27Al-NMR methods, respectively, have been compared and analyzed. The experimental results show that the species distribution and transformation of PASC are different from those of PACl, due to the interaction of polysilicic acid and hydrolyzed aluminum species. At the same basicity (B), the contents of, Al(b), Al13 and the monomer species Almono (also determined by 27Al-NMR) in PASC are lower than those in PACl, while the contents of Al(c) and the Alother determined by 27Al-NMR in PASC are higher than those in PACl. The differences between PASC and PACl with respect to these species enlarge as the molar ratio of Al/Si in PASC decreases. Further, in PACl the ratio of Al13 to Al(b) closes to 1.0, indicating that the amount of the two fractions are similar. In PASC, however, such an agreement does not exist at the lower B values and Al/Si molar ratios. When the B value and Al/Si molar ratios increase, however, the amount of Al13 and Al(b) species tends to close. The study findings indicate that polysilicic acid can react with hydrolyzed aluminum species to form an aluminum silicate polymer composite and result in the change in species distribution of PASC.     

Synthesis of high-purity Na-A and Na-X zeolite from coal fly ash

Coal fly ash (CFA) was used as a raw material for the synthesis of zeolite molecular sieve. The synthesis began with the pretreatment of CFA to remove impurities (e.g., Fe₂O₃, CaO, etc.) under various acid types (HCl, H₂SO₄, and HNO₃) and acid/CFA ratios (5–25 mL_acid/g_CFA). High product purity (up to 97%) was achieved with HCl (20%wt), and acid/CFA ratio of 20 mL_HCl/g_CFA. The treated CFA was then converted to zeolite by the fusion reaction under various Si/Al molar ratios (0.54–1.84). Zeolite type A was synthesized when the Si/Al molar ratios were lower than 1, whereas sodium aluminum silicate hydrate was formed when the Si/Al molar ratio were higher than 1. The highest water adsorption performance of the zeolite product, i.e., the outlet ethanol concentration of 99.9%wt and the specific adsorption capacity of 2.31 × 10^?2 g_water/g_zeolite, was observed with the Si/Al molar ratio of 0.82. The zeolite was tested for its water adsorption capacity repeatedly 10 times without deactivation.

Implications: This work evaluated the technical feasibility in the conversion of CFA to zeolite, which would help reduce the quantity of waste needed to be landfilled. This adds value to the unwanted material by converting it into something that can be further used. The synthesized products were shown to be quite stable as water adsorbent for the dehydration of ethanol solution.     

Toxicity and metal speciation characterisation of waste water from an abandoned gold mine in tropical northern Australia

The decommissioned Mount Todd gold mine, located in the wet-dry tropics of northern Australia, consists of a large waste water inventory and an acid rock drainage problem, which has the potential to impact upon freshwater ecosystems of the Edith River catchment. The toxicity of retention pond 1 (RP1) water was determined using six local freshwater species (duckweed, alga, cladoceran, snail, hydra and a fish). RP1 water was very toxic to all species, with the percentage dilution of RP1 water inhibiting 10% of organism response (IC(10)), or lethal to 5% of individuals (LC(5)), ranging from 0.007 to 0.088%. The percentage dilution of RP1 water inhibiting 50% of organism response (IC(50)), or lethal to 50% of individuals (LC(50)), ranged from 0.051% to 0.58%. Based on chemical analyses and geochemical speciation modelling of the test waters, Cu, Zn and Al were the most likely toxic components at acidic dilutions (i.e. 1%), while Cu and Zn were the most likely toxic components at 0.1% RP1 water, where pH was 6.5. Species sensitivity distributions (SSDs) were used to predict dilutions of RP1 water that would protect or unacceptably affect the downstream aquatic ecosystems. A dilution ratio of 1 part RP1 water to 20000 parts Edith River water (0.005% RP1 water) was calculated to be required for the protection of at least 95% of species. This information can be used in conjunction with field chemical and biological data to better predict the ecological risks of RP1 waste water downstream of the Mount Todd mine.     

Importance of natural soil processes relative to atmospheric deposition in the mobility of aluminium in forested watersheds of the Black Forest

The dynamics of aqueous aluminium in the ARINUS experimental watersheds at Schluchsee (granite) and Villingen (quartz sandstone), Black Forest (South-west Germany), were studied in order to detect the processes and factors controlling its mobility. Aluminium speciation was performed in the seepage of typical soils (podsol, acidic brown earth, stagnogley) at 3 depths (organic layer, 30 cm and 80 cm of the mineral soil) as well as in streamwater. The studies concentrated on the variability in time and space of inorganic monomeric Al (Ali), and organic monomeric Al (Alo). Furthermore, the equilibrium speciation model WATEQF was used to calculate the distribution of inorganic Al species. Natural soil properties and processes, such as DOC mobilization and excess mineralization of NO3(2-) and SO4(2-), appeared to have great influence and outweigh the deposition effects upon Al mobilization in these systems which receive only low to moderate loads of acidic deposition.     

Selenium speciation in acidic environmental samples: application to acid rain-soil interaction at Mount Etna volcano

Speciation plays a crucial role in elemental mobility. However, trace level selenium (Se) speciation analyses in aqueous samples from acidic environments are hampered due to adsorption of the analytes (i.e. selenate, selenite) on precipitates. Such solid phases can form during pH adaptation up till now necessary for chromatographic separation. Thermodynamic calculations in this study predicted that a pH < 4 is needed to prevent precipitation of Al and Fe phases. Therefore, a speciation method with a low pH eluent that matches the natural sample pH of acid rain-soil interaction samples from Etna volcano was developed. With a mobile phase containing 20 mM ammonium citrate at pH 3, selenate and selenite could be separated in different acidic media (spiked water, rain, soil leachates) in <10 min with a LOQ of 0.2 μg L⁻¹ using ⁷⁸Se for detection. Applying this speciation analysis to study acid rain-soil interaction using synthetic rain based on H₂SO₄ and soil samples collected at the flanks of Etna volcano demonstrated the dominance of selenate over selenite in leachates from samples collected close to the volcanic craters. This suggests that competitive behavior with sulfate present in acid rain might be a key factor in Se mobilization. The developed speciation method can significantly contribute to understand Se cycling in acidic, Al/Fe rich environments.     

Distribution of lead, copper and zinc in size-fractionated river bed sediment in two agricultural catchments of southern Ontario, Canada

Metal (Pb, Cu and Zn) partitioning in six separated sediment size fractions (<8, 8-12, 12-19, 19-31, 31-42, 42-60 microm) of river bed sediment have been analyzed by sequential extraction. The concentrations of some major elements (Si, Al, Ca, Mg, K, Na, Fe, Mn and P), and organic and inorganic C were determined to correlate the elemental composition of the sediment with metal speciation and grain size. Results show that Zn and Pb concentrations increase with decreasing grain size. For Big Creek and Big Otter Creek, respectively, the highest concentrations of Zn (326 and 230 mg kg(-1)) and Pb (158 and 67 mg kg(-1)) were found in the smallest (<8 microm) fraction, whereas the Cu levels (619 and 1281 mg kg(-1)) were most abundant in the second smallest (8-12 microm) fraction. The major accumulative phases for Cu, Zn and Pb were carbonates, Fe/Mn oxides and organic matter, but the relative importance of each phase varied for individual metals and grain sizes. The extraction data show increasing potential bioavailability of metals with decreasing grain size. Estimates of metal yields in the study catchments suggest that over 80% of the metal yield in sediment smaller than 63 microm is associated with solids smaller than 31 microm.     

聚硅酸锌铝的制备及其性能研究

以硅酸钠、硫酸锌、硫酸铝为原料,通过共聚法制备了无机高分子絮凝剂聚硅酸锌铝（PSZAS）,研究了Na₂SiO₃的摩尔浓度、活化时间、Al/Si、Zn/Si 配比及絮凝剂的投加量对絮凝效果的影响,用X-射线衍射（XRD）和电子扫描电镜（SEM）对该絮凝剂的结构及形貌进行了表征。结果表明：当硅酸钠的浓度为0.4 mol/L,硅酸活化时间为2 h,Si∶Al∶Zn=1∶1∶1.5,絮凝剂投加量为20 mL/L废水时,絮凝剂的电中和能力和吸附架桥能力最强,絮凝剂对含H-酸染料模拟废水的絮凝效果最好。     

The application of novel coagulant reagent (polyaluminium silicate chloride) for the post-treatment of landfill leachates

Relatively "old" (stabilized) landfill leachates are a special category of wastewaters, which are difficult to treat further, mainly due to their bio-refractory organic content (humic substances). In this study, coagulation-flocculation was examined as post-treatment method for the biologically pre-treated stabilized leachates. The purpose was to examine the coagulation performance of alternative coagulant agents, i.e. the composite coagulant polyaluminium silicate chloride. Composite coagulants with different Al to Si molar ratio and different preparation methods were tested. Their efficiency was evaluated by monitoring from turbidity and phosphate content, other parameters strongly correlated with the presence of organic matter, such as UV absorbance at 254nm, COD and colour. The results suggest that the silica-based coagulants exhibit better coagulation performance, than the relevant conventional coagulant (alum) or simple pre-polymerized coagulants (PACl). Polyaluminium silicate chloride has greater tolerance against pH variation than alum or PACl, whereas this novel coagulant works better at pH values between 7 and 9. Coagulation-flocculation has proved to be an efficient post-treatment method for the biologically pre-treated leachates, promoting the removal of the refractory humic substances, while the treatment efficiency of coagulation can be improved by the application of the new coagulant agent.     

Soil solutions and surface water analysis in two contrasted watersheds impacted by acid deposition, Vosges mountains, N.E. France: interpretation in terms of Al impact and nutrient imbalance

Two acid watersheds in the Vosges mountains (N.E. France), one with a podzol, the other with an acid brown soil, were monitored by analysing soil solutions and two related springs for total chemistry and Al speciation. High concentrations of inorganic Al did not occur in the podzol upper horizons but were evident in the corresponding spring, together with low concentrations of Ca. In the acid brown soil area, high concentrations of inorganic Al occurred in the leaching water draining the upper soil horizons, but not in the undrained water nor in the spring, the latter exhibiting rather high Ca content. In both watersheds, needle yellowing in conifers could be observed and might be ascribed to Mg deficiency rather than to Al toxicity.     

Influence of hydrology on heavy metal speciation and mobility in a Pb-Zn mine tailing

Among the inorganic toxicants of greatest concern in mine tailings, Pb, Zn, Cu, Cd and As figure prominently due to their abundance and potential toxicity. Here we report on their biolability and solid-phase speciation in two sediment cores subject to variable hydrological regimes at an abandoned pyritic mine tailing. The oxic conditions of well-drained sediments induced pyrite oxidation and the subsequent liberation of H+, SO4(2-) and considerable quantities of Fe(III), which precipitated as goethite. Solubility of Pb, Zn, Cu and Cd was closely coupled to pH and goethite presence. Metal lability was particularly low in zones of neutralization, formed by the accumulation of calcite, first carried then deposited by percolating waters in both saturated and unsaturated cores. We conclude that differential hydrology induces variable heavy metal speciation and biolability in Pb-Zn mine tailings, and suggest that site-specific risk assessments must account for past and present hydrological regimes.     

Tissue accumulation of aluminium is not a predictor of toxicity in the freshwater snail, Lymnaea stagnalis

The amount of toxic metal accumulated by an organism is often taken as an indicator of potential toxicity. We investigated this relationship in the freshwater snail, Lymnaea stagnalis, exposed to 500 μg l⁻¹ Al over 30 days, either alone or in the presence of phosphate (500 μg l⁻¹ P) or a fulvic acid surrogate (FAS; 10 mg l⁻¹ C). Behavioural activity was assessed and tissue accumulation of Al quantified. Lability of Al within the water column was a good predictor of toxicity. FAS increased both Al lability and behavioural dysfunction, whereas phosphate reduced Al lability, and completely abolished Al-induced behavioural toxicity. Tissue accumulation of Al was not linked to toxicity. Higher levels of Al were accumulated in snails exposed to Al + P, compared to those exposed to Al alone, whereas FAS reduced Al accumulation. These findings demonstrate that the degree of tissue accumulation of a metal can be independent of toxicity.     

The variations of aluminium species in mountainous forest soils and its implications to soil acidification

Aluminium (Al) speciation is a characteristic that can be used as a tool for describing the soil acidification process. The question that was answered is how tree species (beech vs spruce) and type of soil horizon affect Al speciation. Our hypotesis is that spruce and beech forest vegetation are able to modify the chemical characteristics of organic horizon, hence the content of Al species. Moreover, these characteristics are seasonally dependent. To answer these questions, a detailed chromatographic speciation of Al in forest soils under contrasting tree species was performed. The Jizera Mountains area (Czech Republic) was chosen as a representative mountainous soil ecosystem. A basic forestry survey was performed on the investigated area. Soil and precipitation samples (throughfall, stemflow) were collected under both beech and spruce stands at monthly intervals from April to November during the years 2008–2011. Total aluminium content and Al speciation, pH, and dissolved organic carbon were determined in aqueous soil extracts and in precipitation samples. We found that the most important factors affecting the chemistry of soils, hence content of the Al species, are soil horizons and vegetation cover. pH strongly affects the amount of Al species under both forests. Fermentation (F) and humified (H) organic horizons contain a higher content of water extractable Al and Al³⁺ compared to organo-mineral (A) and mineral horizons (B). With increasing soil profile depth, the amount of water extractable Al, Al³⁺ and moisture decreases. The prevailing water-extractable species of Al in all studied soils and profiles under both spruce and beech forests were organically bound monovalent Al species. Distinct seasonal variations in organic and mineral soil horizons were found under both spruce and beech forests. Maximum concentrations of water-extractable Al and Al³⁺ were determined in the summer, and the lowest in spring.     

Effect of water treatment residuals on soil phosphorus, copper and aluminium availability and toxicity

Water treatment residuals (WTRs) are produced by the treatment of potable water with coagulating agents. Beneficial recycling in agriculture is hampered by the fact that WTRs contain potentially toxic contaminants (e.g. copper and aluminium) and they bind phosphorus strongly. These issues were investigated using a plant bioassay (Lactuca sativa), chemical extractions and an isotopic dilution technique. Two WTRs were applied to an acidic and a neutral pH soil at six rates. Reductions in plant growth in amended soils were due to WTR-induced P deficiency, rather than Al or Cu toxicity. The release of potentially toxic Al from WTRs was found to be mitigated by their alkaline nature and pH buffering capacity. However, acidification of WTRs was shown to release more soluble Al than soil naturally high in Al. Copper availability was relatively low in all treatments. However, the lability of WTR-Cu increased when the WTR was applied to the soil.     

聚硅基复合氯化铁絮凝剂的制备及其在采油废水处理中的应用

采用硅酸钠制备聚硅酸,探讨了活化pH、活化剂、硅酸钠浓度(以SiO_2质量分数计)及聚合温度等因素对聚硅酸稳定性的影响.利用聚硅酸及氯化铁制备聚硅基复合氯化铁(PSiF),并通过正交试验分析了活化pH、Si/Fe(摩尔比)、OH/Fe(摩尔比)、制备时间对PSiF絮凝性能的影响.综合考虑絮凝性能、稳定性以及经济性等因素,确定PSiF适宜的制备条件为SiO_2质量分数2%～3%;活化pH为2～3;Si/Fe为0.50～0.75;OH/Fe为0.50～0.75;制备时间为0.5 h;聚合温度低于25℃.对比PSiF、PAC、FeCl_3对采油废水的处理效果,PSiF除浊、除COD效果以及经济性最好,是一种应用前景广阔的新型絮凝剂.     

The effect of acidification on the accumulation and toxicity of metals to freshwater invertebrates

This paper reviews the literature to determine if lowered water pH (a) affects metal bioaccumulation in freshwater invertebrates, (b) enhances the toxicity of a given metal, and (c) increases waterborne metal concentrations to levels toxic to invertebrates. The elements considered are mercury, lead, cadmium and aluminum. The available evidence suggests that of these elements only mercury is biomagnified in aquatic foodchains. The bioaccumulation of all these elements is influenced by water pH, but data concerning invertebrates is meagre for mercury and lead. The effect of pH on mercury and lead toxicity to invertebrates is unclear and may be largely species specific. Cadmium toxicity is reduced by lower pH, while aluminum toxicity to invertebrates is markedly higher due to changes in aluminum speciation at low pH.     

Latent hydraulic reactivity of blended cement incorporating slag made from municipal solid waste incinerator fly ash

The reactivity of cement pastes made by blending Portland cement with slag from municipal solid waste incinerator (MSWI) fly ash was investigated to assess the potential of recycling MSWI fly ash slag. The slag, prepared by melting MSWI fly ash at 1400 degrees C for 30 min, was pulverized and ground, then blended with ordinary Portland cement (OPC), using various substitution levels to make slag-blended cement (SBC). The pozzolanic reactivity of the ecocement was then characterized by determining variations in the compressive strength, degree of hydration, microstructure, speciation, and mineralogical crystalline phases. The results suggest that the strength of the pastes at an early age decreased with increasing substitution levels, whereas the strength at a later age of the tested pastes (with substitution levels less than 10%) outperformed OPC paste because of typical SBC properties. The development of strength at a later age was also confirmed by X-ray diffraction and scanning electron microscopy techniques. This implies that active silica (Si) and alumina (Al) react with the hydration product, calcium hydroxide (Ca(OH)2), to form calcium silicate hydrate (C-S-H), which contributed to strength development at a later age by the filling up of pores in the SBC pastes. The pozzolanic activity of the SBC pastes indicates that it is suitable for use as a substitute for OPC in blended cement.     

Toxicity of municipal wastewater effluents contaminated by pentachlorophenol in Southwest Missouri

Toxicity of effluents from two sewage treatment plants in Joplin, Missouri, was tested using Ceriodaphnia dubia and Pimephales promelas. No test organisms survived in effluents from either plant, in effluents diluted with water from Turkey Creek (the receiving stream), or in water from Turkey Creek. Mortality was complete in all but the most dilute treatments of effluents, in which reconstituted water was used as the diluent. High concentrations of pentachlorophenol (130-970 microg liter(-1)) in effluents and the receiving stream likely caused mortality during the 7-day tests. Detectable concentrations of other phenolic compounds indicated the presence in Turkey Creek of other toxic by-products of pentachlorophenol manufacture. This study demonstrated the utility of biological tests of whole effluents to determine toxicity of wastewater effluents.     

中孔分子筛Al-MCM-41催化裂解聚烯烃反应研究

采用水热合成法制备了不同硅铝比的中孔分子筛A l-MCM-41,将其应用于高密度聚乙烯(HDPE)和聚丙烯(PP)的催化裂解反应。通过改变硅铝比、反应温度和催化剂用量,对A l-MCM-41催化HDPE和PP裂解反应的规律进行了探讨,研究表明,HDPE裂解反应受硅铝比的影响较大;而对于PP裂解反应,硅铝比在一定范围内对催化剂活性的影响不明显。另外,与热裂解和HZSM-5小孔分子筛的催化裂解结果进行了比较,结果证明A l-MCM-41具有较高的催化活性和较高的液体产物收率,尤其适合于空间位阻较大的PP的催化裂解反应。