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.     

Accumulation of aluminium by the freshwater crustacean Asellus aquaticus in neutral water

This study examined the accumulation of aluminium (Al), mostly as the insoluble (Al(OH)(3)) species, by the freshwater crustacean Asellus aquaticus at neutral pH. Animals were exposed to a range of Al concentrations (5-356 microg l(-1)) in three experiments. The first two were of 30 and 50 days duration, respectively, followed by transfer of the A. aquaticus to water containing no Al for 20 days. The third used live and dead animals in order to investigate the contribution made by surface adsorption of Al to the total accumulated. Significant accumulation of Al in the whole tissues occurred by day 10 in all animals in the 30- and 50- day experiment. Peak concentrations of Al were measured in animals between days 10 and 20 with high concentration factors ranging from 1.4 x 10(4) to 5.5 x 10(3). By day 30, accumulated Al had fallen but was still significantly greater than the control in the 50- day exposure experiment. This 30- day increase followed by decreased accumulation of Al was repeated over the remaining exposure period (i.e. 30-50 days) although rates of uptake and loss and peak tissue levels of Al were higher. Proportionality between environmental (water) and tissue concentrations of Al occurred at day 20 but not at day 45. Significantly more Al was accumulated by dead animals than live animals at all Al exposure concentrations. These results suggest that Al is available to the crustacean at neutral pH and that the cuticle may provide an important site of uptake.     

Bioaccumulation of aluminium in the freshwater snail Lymnaea stagnalis at neutral pH

This study examined the accumulation of aluminium (Al) by the freshwater snail Lymnaea stagnalis at neutral pH, when most Al would be predicted to be in an insoluble form (Al(OH)(3)). Snails were exposed to a range of Al concentrations (38-285 microg l(-1)) for 30 days, followed by 20 days in clean water. Aluminium was measured using atomic absorption spectroscopy. Significant accumulation of Al occurred in the whole soft tissues, gut, digestive gland and kidney at the latest by day 10. High concentration factors were observed, ranging from 4.5 x 10(3) in the whole soft tissues to 6.3 x 10(4) in the kidney, corresponding to actual concentrations of 800 to 7500 microg g(-1), respectively. Proportionality between environmental (water) and tissue concentrations of Al was observed in the gut but not in the other tissues. Following transfer to clean water, rapid loss of Al from the whole soft tissues and gut was seen over the first 10 days. Loss of Al from the digestive gland was much less as a proportion of the total, with approximately 90% of the Al remaining in the tissue. In contrast, significant loss of Al from the kidney occurred between days 20 and 30, even in the continued presence of Al; little further loss occurred following transfer to clean water. Aluminium is clearly available to the snail at neutral pH, the most likely route of entry being the gut. This could facilitate entry of the metal into the food chain. The possible roles of the digestive gland and kidney in the handling of Al are discussed.     

Effects of aluminium in acid streams on growth and sporulation of aquatic hyphomycetes

We investigated, by field and laboratory experiments, the effects of aluminium in an acid stream (pH 5.0) on the growth and sporulation of aquatic hyphomycete fungi which degrade organic litter. The stream water had monomeric aluminium (Al(m)) concentrations of 9.1-13.4 microm - fifty times higher than a nearby circumneutral stream. Alder leaves submersed in the stream accumulated Al, most of which was tightly bound. Growth rates of four species of aquatic hyphomycetes were altered by inclusion of Al(m) in the culture medium. On a polypectate substrate, and on low-phosphate medium with glucose, growth rates increased significantly. On a low-nutrient substrate of homogenized alder leaves, growth rates were inhibited by aluminium. The pattern of mycelial growth was found to be different on a polypectate medium including Al(m), compared with a control without aluminium. There was a significant increase in hyphal radial growth and a decrease in the hyphal growth unit. The effect resembled the growth of a starved fungal colony. Treatment with Al(m) decreased pectinase production by the four fungal species tested. The capacity of these species to sporulate was reduced by flooding culture plates with Al(m) solution. These deleterious metabolic effects were most severe in isolates taken from circumneutral streams and less marked, though significant, in species originating from acid streams.     

新型絮凝剂含硼聚硅铝铁的制备和性能研究

向聚硅酸中引入Al³⁺、Fe³⁺、B,制得稳定性更好的高效絮凝剂含硼聚硅铝铁（PFASB）。通过实验得到其最佳配比为：n_(B)/n_(Si)=0.16、n_(Fe)/n_(Al)=0.5 、n_(Al+Fe)/n_(Si)=1。对造纸废水和焦化废水进行混凝实验表明,PFASB的除浊、除COD的能力均优于聚合铝、聚合铝铁和聚硅铝铁,而且矾花产生迅速,矾花粗大密实,是一种性能优异的新型高分子絮凝剂。实验还考察了絮凝剂的形貌和结构,结果表明B、铝及其水解产物、铁及其水解产物和聚硅酸等多种组分之间有相互作用,形成了尺度更大的聚集单元。PFASB的这种特殊结构是其具有良好稳定性和混凝性能的根本原因。     

Effects of clearfelling on stream and soil water aluminium chemistry in three UK forests

Data are presented demonstrating how clearfelling has changed soil and stream water aluminium chemistry. For soil waters, a strong empirical relationship was observed between inorganic aluminium (Al(inorg)) and total inorganic anion (TIA) concentrations. Before felling, chloride and sulphate accounted for the largest proportion of the TIA concentration. After felling, in soils where nitrification was active, nitrate became increasingly important. Where this led to an increase in TIA, Al(inorg) concentrations increased. Over five years, nitrate concentrations have fallen, along with TIA, resulting in a sympathetic decline in Al(inorg). Streams draining clearfelled areas initially became more acid, although chloride and sulphate concentrations decreased. Stream water nitrate concentrations increased soon after felling and remained higher than controls for up to four years. While nitrate concentrations were high, Al(inorg) remained unchanged. Subsequently, as nitrate and TIA decreased, Al(inorg) also declined to concentrations below those in the control stream. Clearfelling upland forests will not necessarily result in immediate improvements in water quality, although long-term benefits may be seen before canopy-closure of the next crop.     

Adsorption of aluminium by stream particulates

An experimental study was made of the adsorption of aluminium by fine particulates from Whitray Beck, a hill stream in NW England. Adsorption increased with Al(3) activity, pH and concentration of particles, and could be quantitatively described by the empirical equation: [Formula: see text] [particles] where square brackets indicate concentrations, curly brackets, activities, and alpha, beta and gamma are constants with values of 5.14x10(-10) (mol litre(-1))(2.015) (g particles litre(-1))(-1), 0.457, and 1.472, respectively. For the experimental data, the equation gave a correlation ratio of 0.99. The equation accounts reasonably well for the adsorption of Al by particulates from seven other streams. In applying the equation, it must be borne in mind that the desorption kinetics of Al depend on pH, and rapid reversibility (<15min) can only be assumed for pHor=10%) of total monomeric Al.     

The influence of plantation forestry on the pH and aluminium concentration of upland welsh streams: a re-examination

Previous studies relating forest presence to stream acidity and aluminium concentration were based on small numbers of catchments, often precluding the elimination of confounding influences on stream chemistry, such as geology or soil type. Spatial patterns in aluminium and pH data from 113 Welsh catchments of contrasting land use were therefore analysed in three different ranges of acid sensitivity (< 10, 10-15, 15-25 mg CaCO(3) litre(-1) total hardness). In each range, pH declined and aluminium increased significantly with increasing percentage forest cover. There was no evidence that the relationships reflected a spurious effect of forest location. Where aluminium concentrations were elevated under forest in a sub-set of 13 streams, aluminium was present predominantly in the labile form, most toxic to fish. Regressions of pH and aluminium on percentage forest cover provide a useful method of assessing the amount of forest in Welsh catchments which might give rise to given chemical conditions (e.g. pH <6, Al > 80 microg litre(-1)), though some difficulties are likely in accurately specifying the conditions desirable for fish or other biota.     

聚合氯化铝铁的形态分布对微污染源水混凝效果的影响

针对微污染源水中浊度、叶绿素a等的强化去除问题,研究了碱化度、铝铁比和加碱方式等对聚合氯化铝铁形态分布的影响,并考察了形态分布与混凝除污效率和混凝沉淀出水中残铝浓度的关系.结果表明:在铁摩尔分数一定时,混凝剂中单体、中等聚合物和无定形凝胶含量与碱化度存在线性相关性,并推导出中等聚合物含量的计算公式;在碱化度一定时,混凝剂中单体、中等聚合物和无定形凝胶含量与铁摩尔分数也存在线性相关性;增加碱化度或降低铁摩尔分数,可以增加中等聚合物含量、降低单体含量,从而影响混凝除污效率和混凝沉淀后出水中残铝浓度.混凝实验结果表明,混凝过程中叶绿素a去除率和浊度去除率均与混凝剂中中等聚合物含量存在线性相关性,但两者相关系数不同.混凝沉淀后出水中残铝浓度与混凝剂中单体含量存在线性相关性.因此,预聚合的无机高分子混凝剂对提高混凝过程中的除浊、除藻效率,降低混凝沉淀后出水中残铝浓度具有重要的意义.     

Chemical and biological effects of acid, aluminium and lime additions to a Welsh Hill-stream

Chemical and biological responses to simultaneous additions of acid, aluminium and lime were investigated in contiguous 250m-reaches of a chronically acidic stream in Wales. Treatments were applied for 24 h, and from the upstream end were as follows: zone A-untreated, pH 5.0, 0.37 mg litre(-1) filterable Al; zone B-acidified to pH 4.5, 0.40 mg Al litre(-1) (47% of Al attributed to release from the stream bed due to acid additions); zone C-acidified to pH 4.5 and Al dosed to 0.67 mg litre(-1); zone D-dosed with limestone slurry, resulting in pH 7.2, 0.13 mg Al litre(-1). In all reaches, the chemistry of the interstitial water at depths of 0.15 and 0.3 m never fell below pH 5.5, with corresponding decreases in Al and increases in base cation concentrations. Brown trout, Salmo trutta, and crayfish, Austropotamobius pallipes, held in the stream showed decreases in plasma [Na(+)] and haemolymph [Na(+)], respectively, in all acidic zones (A, B, C): these responses were mitigated by liming (zone D). Thus both chronic and simulated episodic levels of pH and dissolved Al were sub-lethally toxic to test species of aquatic fauna. This experiment also demonstrates a stream bed source/sink of Al, and the availability of a possible refuge from acidic surface waters within the substratum.     

Fluoride and aluminium concentrations of tea plants and tea products from Sichuan Province,PR China

Some Tibetans in Sichuan Province in southwestern China have been suffering from fluorosis, due to drinking and eating tea with high fluoride (F) and aluminium (Al) contents. Tea plants, soils of tea plantations and tea products from Yaan, Gaoxian and Yibin Cities in Sichuan Province were investigated to evaluate the factors affecting F and Al contents in tea products. The F and Al concentrations of four commercial brands of brick teas were significantly higher than those of 11 brands of green teas. Chemical analysis indicated that total and available F and Al concentrations in tea plantation soils in Yaan and Gaoxian were within the normal range compared with acid soils in South China and tea soils in Fujian Province. Edaphic conditions did not contribute to the high F and Al concentrations in brick tea. Analysis of raw materials of brick tea indicated that old leaves were the major contributors to the high F and Al contents contained in brick tea. There were also great variations among different tea varieties in accumulating F and Al, and concentrations of F and Al in tea variety of Qianmei 303 were about 2-3-fold higher than the other three varieties. Selection of appropriate varieties would be important to lower F and Al contents in tea products.     

Improvement of coagulation-flocculation process using anionic polyacrylamide as coagulant aid

A physicochemical treatment (coagulation-flocculation) was applied to a slaughterhouse wastewater, using anionic polyacrylamide as coagulant aid to improve the settling velocity of the flocs formed with the coagulants used: ferric sulphate, aluminium sulphate and polyaluminium chloride. The optimum speed and stirring time for the flocculation stage were ascertained along with the optimum pH and coagulant and coagulant aid doses. The speed and coagulation time were initially set according to recommendations in the literature concerning the treatment of this type of water. Chemical oxygen demand (COD), biochemical oxygen demand at 5 days (BOD5) and total suspended solids (TSS) were recorded at the beginning and end of each experiment in order to monitor the process. Once the optimal conditions had been established, several parameters were measured in order to assess the coagulation-flocculation process: particle number and size, sludge volume, nutrients (ammonia nitrogen, total Kjeldahl nitrogen, albuminoid nitrogen, orthophosphate, total phosphorus) and the residual concentration of iron and aluminium in clarified water. Anionic polyacrylamide, when added with ferric sulphate or polyaluminium chloride led to a significant increase in the settling speed.     

Photochemically induced formation of the "Al13" tridecameric polycation in the presence of Fe(III) and organic acids

We found that light-induced Fe(III) reduction associated with the oxidation of a simple hydroxy-carboxylic acid (lactate) caused the formation of the AlO4Al12(OH)24(H2O)12 polycation ("Al13"). Initial conditions were a lactate:Al:Fe ratio of 1:0.76:0.11 in a partially neutralized solution. Base was added rapidly and no Al13 was detected in samples kept in the dark. With exposure to light, Fe(III) reduction was rapid and Fe(II) reached a maximum within 1 day. After the maximum, steady-state Fe(II) declined from 54% to 43% over eight days. During this same time period, the lactate concentration fell to 2% of the original, pH rose from 4.05 to 4.46, and the Al13 detectable by 27Al NMR increased to 2.3 mmol l(-1) (51% of the total solution Al). The formation of Al13 is attributed to the pH rise resulting from the removal of the organic acid buffer. Similar photo-induced chemical changes occur in natural waters and may promote the formation of Al13, conditions permitting.     

Thermolysis of 2,4,6-trichlorophenol chemisorbed on aluminium oxides as example of fly ash mediated surface catalysis reaction in PCDD/PCDF formation

The influence of aluminium cation as a strong electrophilic centre on the thermolysis of chlorophenols chemisorbed on Al(OH)₃ surface was investigated. If thermolysis is carried out at 300 °C the spontaneous rupture of the bond between aluminium and oxygen of phenol takes place in the temperature range of 260–280 °C. The thermolysis of chlorophenoxy aluminium compounds occurs through homolytic and heterolytic bond cleavage. In the case of heterolytic cleavage the leaving chlorophenoxy anion causes a simultaneous formation of the aluminium cation, which is the driving force for the rearrangement of the unstable intermediate. By homolytic cleavage of the Al–O bond the chlorophenoxy radical is formed. The isolation of reaction products of the thermolysis of the system Al(OH)₃/2,4,6-trichlorophenol gave five isomers of dimeric compounds of resonance stabilised 2,4,6-trichlorophenoxy radical. The compounds are stable in nonaqueous, aprotic solution, but they are very sensitive to acid catalysis. They quickly transform into aromatic hydroxydiphenyl ethers. The process of dechlorination and aromatisation of cyclohexadienone dimers gives PCDD/PCDF.     

复合型聚合硅酸絮凝剂的制备及其除浊除磷性能研究

在聚合硅酸中同时引入铁、镁或铁、钙2种金属离子,制成复合型聚合硅酸絮凝剂;研究了其除浊、除磷的最佳絮凝条件,包括絮凝剂投加量、水样pH值对浊度和磷去除率的影响;采用喹啉重量法测定了各种絮凝剂形成的絮体中磷的含量.结果表明,当铁磷摩尔比为2.5～3.0,pH值为7.0～8.5时,对浊度和磷的去除率最高,均达99.0%以上,聚合硅酸镁铁(PSAMF)絮凝剂适合用于磷回收.     

The mixing zone between limed and acidic river waters: complex aluminium chemistry and extreme toxicity for salmonids

When liming running waters, dosers must compensate for different flow and water qualities and for the downstream inflow from acid tributaries which creates mixing zones. At a certain point in the mixing zone, a constant or fluctuating chemical disequilibrium will appear due to transformation processes. In laboratory assays, over-saturated solutions of aluminium with ongoing active precipitation of aluminium have been found to be especially toxic to fish. Recent experiments in a mixing zone in the limed River Audna, Norway, have confirmed this phenomenon. Atlantic salmon (Salmo salar L.) and sea trout (Salmo trutta L.) smolts were exposed to acid and limed waters and mixtures of the two waters downstream from the point of connection. In the acid tributary (mean values: pH=4.8, Ca=1.3 mg litre (-1)), Ali 236 microg litre(-1)=), LT5) was 22 and 40 h for Atlantic salmon and sea trout, respectively. In the mixing zone (pH=4.8-6.5, Ca=1.2-3.2 mg litre(-1), Ali=50-240 microg litre(-1)), LT50 was 7 h for both species, masking the normal species difference in tolerance. Osmoregulatory failure and rapid gill lesions occurred in the mixing zone as an effect of the transformation of Al into high molecular weight precipitating species. This is the first documentation of the existence of such highly toxic mixing zones in nature, and the results clearly show that the mixing zone is even more toxic to fish than acid aluminium-rich waters.     

Effect of fluoride on the amount of aluminium dissolved by boiling fruit acids

Boiling citric and tartaric acids dissolved aluminium from sheets and pans made of this metal. Fluoride increased the amount of aluminium dissolved by both citric and tartaric acids at the sort of concentrations which might be used in normal cookery (0.2%, pH 2.6). Increasing the amount of fluoride increased the amount of dissolved aluminium. The proportional increase was greater at low fluoride levels. Acids varied in their individual effects; tartaric acid dissolved considerably more aluminium than citric acid under any given set of conditions. The longer an acid solution was boiled with aluminium, the more of the metal dissolved. Repeated boiling of aluminium in acid solutions did not necessarily alter its response to further boiling. Old pans were attacked more strongly by acid solutions when fluoride was present. The precise composition of the aluminium metal used did not affect any of these conclusions.     

Effects of aluminium ion on root growth, cell division, and nucleoli of garlic (Allium sativum L.)

The effects of different concentrations of aluminium chloride on root growth, cell division, chromosome morphology and nucleoli in root tip cells of garlic (Allium sativum L.) were studied. The concentrations of aluminium chloride (AlCl(3)) used were 10(-5), 10(-4), 10(-3), 10(-2) and 10(-1) m. Aluminium chloride inhibited root growth and caused mitotic irregularities, including c-mitosis, anaphase bridges, and chromosome stickiness. Nucleolar material was extruded from the nucleus into the cytoplasm. Extrusion was observed in inner root meristem and root cap cells. The poisoning by Al(3+) of the root tip cells of Allium sativum may result from the uptake and accumulation of Al and inhibition of Ca uptake, distribution of physiological activities of calmodulin (CaM) and the inhibition of some enzyme reactions.     

Functional and structural rearrangements of salivary gland polytene chromosomes of Chironomus riparius Mg. (Diptera,Chironomidae) in response to freshly neutralized aluminium

Although recent work has shown that environmentally relevant concentrations of freshly neutralized aluminium (AI) are bioavailable and toxic to freshwater invertebrates, the genotoxicity of Al has not been examined. Here we show that freshly neutralized Al affects structure and function of the salivary gland polytene chromosomes of the ubiquitous chironomid larva Chironomus riparius over three generations. Exposure to 500 microg l-1 added Al for 24-25 days resulted in a significantly higher frequency of numerous somatic aberrations, while no structural aberrations were found in F1 controls and few in the second and third generation. Aberrations also included deletions of sections of chromosome G of C. riparius larvae as well as deletions of one or more Balbiani rings. Changes in functional activity included decreased activity of the Balbiani rings (BR), and an increase in the number of decondensed centromeres. The activity of the nucleolar organizer (NOR) significantly decreased in F1 chironomids exposed to Al, while in the F2 and F3 generations the NOR showed normal (high) activity. First generation chironomids were generally more susceptible to Al although no clear evidence of tolerance was apparent over three generations. The possible use of alterations in chironomid polytene chromosomes as biomarkers of trace metal pollution is discussed.     

Removal of pesticides from surface waters by combined physicochemical processes. Part I: Dodine

The simultaneous action of powdered activated carbon and several coagulant agents on the removal of the fungicide dodine from spiked distilled water, was studied. As coagulants, ferric chloride (FeCl₃) and basic polyaluminium chlorosulfate ([Al(OH)_xCl_y(SO₄)_z]_n) were examined, using polyacrylamide, in certain cases, as coagulant aid (polyelectrolyte). The efficiency of dodine removal was investigated with respect to the added amount of powdered activated carbon (PAC), the pH value, as well as the type and dose of coagulant and polyelectrolyte. The experiments were performed applying the standard jar-test procedure. The initial concentration of dodine was 250 μg/L. At this concentration and pH range 5–8 it was found that a dose of 100 mg/L PAC was necessary to achieve more than 98% removal of dodine, whereas lower removal (91–93%) was obtained applying half the dose of PAC under the same conditions. However, when 10–100 mg/L FeCl₃ were simultaneously added with PAC, the removal efficiency increased to >98%, even with the half PAC dose.