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.     

Benthic macroinvertebrate community structure in 20 streams of varying pH and humic content

The structure of stream benthic macroinvertebrate communities in relation to pH and humic content was studied in 20 second and third-order forest streams in southern Sweden. Streams varied in pH from 4.2 to 8.0, and in humic content from a colour of 5 to 1200 mg Pt litre(-1). There was a positive relationship between pH and species richness, with a discontinuity occurring at pH approximately 5.7. At pH > 5.7, species richness decreased with increasing colour. At pH < 5.7 there was a positive correlation between species richness and humic concentration up to a colour of about 200-300 mg Pt litre(-1). this may be explained by high concentrations, 0.4-0.9 mg litre(-1), of labile monomeric Al occurring in the low coloured acid streams. In streams with a colour > 200 mg Pt litre(-1) labile monomeric Al was less than 0.2 mg litre(-1). There was no significant change in species richness above this threshold, but a shift in species composition towards a dominance of Plecoptera and Chironomidae. This threshold model seems to explain the observed differences in stream benthic community structure better than a simple linear relationship with pH or humic content.     

Soil solution nitrogen and cations influenced by (NH4)2SO4 deposition in a coniferous forest

The effects of chronically enhanced (NH(4))(2)SO(4) deposition on ion concentrations in soil solution and ionic fluxes were investigated in a Picea abies plot at Grizedale forest, NW England. Soil cores closed at the base and containing a ceramic suction cup sampler were 'roofed' and watered every 2 weeks with bulk throughfall collected in the field. Treatments consisted of the inclusion of living roots from mature trees in the lysimeters and increasing (NH(4))(2)SO(4) deposition (NS treatment) to ambient + 75 kg N ha(-1) a(-1). Rainfall, throughfall and soil solutions were collected every 2 weeks during 18 months, and analysed for major cations and anions. NO(3)(-) fluxes significantly increased following NS treatment, and were balanced by increased Al(3+) losses. Increased SO(4)(2-) concentrations played a minor role in controlling soil solution cation concentrations. The soil exchange complex was dominated by Al and, during the experimental period, cores of all treatments 'switched' from Ca(2+) to Al(3+) leaching, leading to mean [Formula: see text] molar ratios in soil solution of NS treated cores of 0.24. The experiment confirmed that the most sensitive soils to acidification (through deposition or changing environmental conditions) are those with low base saturation, and with a pH in the lower Ca, or Al buffer ranges.     

Artificial acidification of a non-acidic and an acidic headwater stream in Maine, USA

Two headwater streams with low DOC and different pHs (4.5-4.8 and 5-6.5) were acidified with H2SO4 to pH 4.1 and 4.5, respectively, for 24-h periods. Neutralization of the added acid occurred by protonation of ANC (HCO3-dominated in the higher pH stream), desorption of Ca (< 15 microeq litre(-1)) and Mg (<6 microeq litre(-1)), and desorption and dissolution of AL (<250 microg litre(-1)) from the stream bed. The concentrations of dissolved organic carbon (DOC) remained constant within the experimental reaches. The concentrations of Na, K an H4SiO4 also remained constant, indicating no detectable increase in the rate of chemical weathering in the stream bed. After acid addition was stopped, concentrations of Ca, Mg and Al decreased to below background, indicating reversible ion exchange as the principal mechanism for the mobility of Ca and Mg and to a lesser extent for Al. Repeated acidifications indicated that significant regeneration of cations on the exchange surfaces of the stream substrate occurs rapidly.     

Reproductive status, blood chemistry, gill histology and growth of perch (Perca fluviatilis) in three acidic lakes

Perch (Perca fluviatilis L.) were sampled soon after spawning in three small acidic lakes (pH 4.3-6.1, Al(lab) 5-106 microg litre(-1), Ca2+ 0.01-0.08 mmol litre(-1)) and in one circumneutral lake (pH 5.9-6.4, Al(lab) 4-12 microg litre(-1), Ca2+ 0.06-0.07 mmol litre(-1)) in southern Finland. Due to the delayed spawning of perch in the acidic lakes, sampling in those lakes was performed later than in the reference lake. In spite of that, the gonadosomatic index (GSI) of males in all the acidic lakes was significantly greater than in the reference lake. Of the two lakes with similar low water pH, the effects on reproduction were more prominent in the lake with higher water Al content. The plasma Ca2+ concentrations of females in the acidic lakes were significantly smaller than in the females of the reference lake. The low female:male plasma Ca2+ ratio (1.0-1.32) depicted delay of spawning. Stress in perch in acidic water was also seen in elevated blood haematocrit values, especially in females. On the other hand, a low plasma Cl- level, a common response to acidic water in salmonids, was not detected in perch in the most acidic lakes. The amount of Al accumulated in the gill epithelium was highest in the most acidified lake with high Al concentration, but was also pronounced in a lake with low pH and low Al concentration.     

Waste Fe(III)/Cr(III) hydroxide as adsorbent for the removal of Cr(VI) from aqueous solution and chromium plating industry wastewater

Fe(III)/Cr(III) hydroxide, a waste material from the fertilizer industry, has been used for the adsorption of Cr(VI) from aqueous solution, over a range of initial metal ion concentrations (5-30 mg litre(-1)), agitation times (1-180 min), adsorbent dosages (100-1200 mg per 50 ml), temperatures (24, 29 and 38 degrees C) and pH values (4.5-10). The adsorption of Cr(VI) increased with the initial concentration of Cr(VI) and with temperature. The process of uptake follows both the Langmuir and the Freundlich isotherm models. The applicability of Lagergren and empirical kinetic models has also been investigated. Almost quantitative removal of Cr(VI) at 10 mg litre(-1) in a 50-ml solution by 500 mg of adsorbent was found at an equilibrium pH of 5.6. The efficiency of chromium removal was also tested using wastewater from the chromium plating industry.     

Unavailability of polynuclear aromatic hydrocarbons from coal particles to the eastern oyster

The accumulation by oysters of polycyclic aromatic hydrocarbons (PAH) from coal dust entering the estuarine environment has been postulated in the vicinity of coal transfer operations. Oysters Crassostrea virginica were exposed to coal dust plus 15 day leachate at concentrations of 10 mg litre(-1) and 1 mg litre(-1) coal dust for 28 days in a flow-through test system. Potential effects of the exposures were measured by comparing the uptake of PAH and the growth of the exposed animals versus control groups. Oysters sampled at 7, 14 and 28 days did not exhibit an increase in PAH body burden over control animals provided the guts were first purged of particulates. Even at the high test concentrations (10 mg litre(-1)), no effect of the exposure on shell growth was observed.     

层状氢氧化镁铝对偶氮染料酸性黑10B的脱色性能研究

分别用层状氢氧化镁铝(LDH)和焙烧层状氢氧化镁铝(CLDH)作为吸附剂吸附脱除水溶液中偶氮染料酸性黑10B.考察了脱色时间、pH值、吸附剂的投加量、温度、染料初始浓度和焙烧温度等因素对脱色率的影响.结果表明,LDH及CLDH对酸性黑10B染料具有良好的脱除效果,室温下,10g/L LDH和1g/L的CLDH对浓度为100mg/L的染料的脱色率分别达95.93%和99.97%.pH值是影响吸附能力的关键因素,吸附剂对溶液pH值有一定缓冲作用.LDH及CLDH对酸性黑10B吸附结果符合Langmuir吸附等温式.饱和吸附后的LDH及CLDH用高温热解法再生,吸附性能良好,随再生次数增多,脱色率下降.     

焙烧态锂铝水滑石对水中氟离子吸附性能研究

采用尿素水热法合成了不同摩尔比的锂铝水滑石(Li/Al LDHs),经480℃煅烧后制备出焙烧态锂铝水滑石(Li/AlLDOs)。研究了Li/Al LDOs对水中氟离子的吸附性能,分别考察了吸附时间、吸附温度和pH等因素对吸附效果的影响,并对吸附机制进行了探讨。结果表明,Li/Al LDOs吸附水中氟离子的行为符合准二级动力学方程,吸附等温数据符合Freundlich吸附等温方程,pH对吸附效果影响较大。X射线衍射分析表明,水滑石样品经历了物相转变及重构过程,Li/Al LDOs可有效去除水体中的氟离子。     

硫酸铝渣去除水中磷研究

分别以蒸馏水和太湖水为例,研究了硫酸铝渣去除水中磷的能力,并分析了其对水体Al3+、SO24-以及pH的影响.结果表明:(1)除太湖水pH为9.0、10.0两种条件外,随着磷平衡浓度的增加,硫酸铝渣除磷量趋于某一定值,其规律符合Langmuir吸附等温式;太湖水pH为9.0、10.0两种条件下,硫酸铝渣除磷量符合Fre...     

Modeling interactions of Hg(II) and bauxitic soils

The adsorptive interactions of Hg(II) with gibbsite-rich soils (hereafter SOIL-g) were modeled by 1-pK surface complexation theory using charge distribution multi-site ion competition model (CD MUSIC) incorporating basic Stern layer model (BSM) to account for electrostatic effects. The model calibrations were performed for the experimental data of synthetic gibbsite-Hg(II) adsorption. When [NaNO(3)] > or = 0.01M, the Hg(II) adsorption density values, of gibbsite, Gamma(Hg(II)), showed a negligible variation with ionic strength. However, Gamma(Hg(II)) values show a marked variation with the [Cl(-)]. When [Cl(-)] > or = 0.01M, the Gamma(Hg(II)) values showed a significant reduction with the pH. The Hg(II) adsorption behavior in NaNO(3) was modeled assuming homogeneous solid surface. The introduction of high affinity sites, i.e., >Al(s)OH at a low concentration (typically about 0.045 sites nm(-2)) is required to model Hg(II) adsorption in NaCl. According to IR spectroscopic data, the bauxitic soil (SOIL-g) is characterized by gibbsite and bayerite. These mineral phases were not treated discretely in modeling of Hg(II) and soil interactions. The CD MUSIC/BSM model combination can be used to model Hg(II) adsorption on bauxitic soil. The role of organic matter seems to play a role on Hg(II) binding when pH>8. The Hg(II) adsorption in the presence of excess Cl(-) ions required the selection of high affinity sites in modeling.     

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.     

Aluminium speciation in surface waters from a Welsh upland area

The complete aluminium speciation of surface waters from an acidified catchment, during dry weather and during storm episodes, is obtained. For the first time, estimates of adsorbed aluminium (Al(ad)) are reported together with other aluminium species. Al(ad) is calculated from the difference between monomeric aluminium content before and after separation of suspended solids by filtration (0.015 microm pore diameter). This fraction was very significant (Al(ad) >; 40 microg litre(-1)) for samples with high suspended solids content (ss >; 20 mg litre(-1)) collected during storm episodes. Plots of pAl(3+) versus pH for samples collected during dry weather are approximated by a straight line, close to the solubility line of synthetic gibbsite, and have a slope of 2.5, which suggests that these samples were saturated with respect to gibbsite. The cloud of pAl(3+) versus pH points for samples from storm episodes has a near zero slope, and shows a significant degree of undersaturation with respect to synthetic gibbsite. Various mechanisms of aluminium mobilisation are discussed.     

The impact of inorganic tin on the planktonic cyanobacterium Synechocystis aquatilis: the effect of pH and humic acid

The influence of inorganic tin compounds on the unicellular cyanobacterium Synechocystis aquatilis was studied, and its dependence on changing pH of the surrounding medium and the presence of humic acid. Both Sn(II) and Sn(IV), used as chlorides (at the concentrations 1-10 mg litre(-1)), inhibit the growth and chlorophyll a content of the cyanobacterium cultures, but only under alkaline conditions. Generally, the observed tin toxicity increased with increase of metal concentration, time of exposure and pH value of the medium (in the range 7-9.8). Sn(II) seems to be more toxic than Sn(IV). At the lowest studied metal concentration (1 mg litre(-1)), Sn(II) caused a 36 and 40% decrease in growth and chl a content, respectively, after 96 h exposure at pH 9.8, while Sn(IV) caused even a slight increase of both physiological parameters (hormetic effect). Similar increases in growth and chl a content were also observed at a high Sn (II) and Sn(IV) concentration (10 mg litre(-1)), but only in cultures exposed to metal at pH 7. At high pH (9.8), 10 mg litre(-1) of Sn(II) and Sn(IV) significantly suppressed both the growth of the cyanobacterium (by 54.2 and 26.1%, respectively) and the chl a content in cultures (by 58.2 and 24%, respectively). Humic acid reduced the toxicity of tin towards the cyanobacterium. The observed effects of pH and complexing ligand on the inorganic tin toxicity are discussed in the context of changing, chemical metal speciation and bioavailability.     

The impact of aluminium on green algae isolated from two hydrochemically different headwater streams, Bavaria, Germany

Two strains of green algae (Scenedesmus sp. and Chlorella sp.) have been isolated from two headwater streams differing in stream chemistry (Eger river: acidic, low alkalinity; Püttlach river: slightly alkaline, high alkalinity). In this study the growth response of these indigenous algae to increased concentrations of aluminium (Al) is investigated. A semi-continuous culture technique was used for Al-toxicity studies. Algal response was determined by calculating growth rates from turbidity and cell counts. Those Al-species which are well known to be toxic were estimated by equilibrium calculations using the WATEQ computer program (Truesdall & Jones, 1973). The pH-value of the culture media was usually pH=5, except for one of the test series. Tested concentrations ranged from c=4 to 220 micromol litre(-1). The isolated strains of green algae were highly sensitive to increased Al-concentrations. The strain isolated from the Püttlach river was more sensitive than the Eger river algae. A total growth inhibition occurs at Al-concentrations of c=4 micromol litre(-1) if the whole Al was added at once. If Al was added gradually into the growth media the response of the algae was delayed. This is due to Al-enrichment in cells. In our long term toxicity studies, growth inhibition occurs even at nearly neutral pH-conditions (pH=6.5) although Al toxicity is expected at pH-values less than pH=5.5. This new result confirms the need of long-term studies in continuous cultures under simulated natural conditions. This might be the only way to achieve valid conclusions about the fate and the toxicity of environmental pollutants.     

Changes in gill morphology of Atlantic salmon (Salmo salar) smolts due to addition of acid and aluminum to stream water

One-year-old Atlantic salmon smolts were held in three artificial channels adjacent to a softwater (mean sp. cond. 30 microS cm(-1), circumneutral stream. Water in one channel was untreated (mean pH 6.25); the others received additions of acid (to mean pH 5.6), or acid plus aluminum (to mean pH 5.5; mean exchangeable Al 158 microg litre(-1)). Gills were sampled after 16 and 23 days of exposure for morphometric examination. On primary lamellae, chloride cells were more numerous in both experimental treatments than in controls. In contrast, numbers of chloride cells on secondary lamellae were elevated only in fish exposed to acid without added Al. Chloride cell size and shape also varied with time and treatment. Fewer gill mucous cells were found in fish exposed to acid plus Al than in controls. Chloride cell proliferation and structural changes may represent an attempt to compensate for increased ionic effluxes with low pH stress by increasing uptake. However, if Al concentrations are high, chloride cells do not proliferate along the secondary lamellae, or proliferating cells are damaged and lost. This may limit the potential to increase ionic uptake.     

鼓泡反应器中液相络合催化同时脱硫脱硝的研究

在鼓泡反应器中考察了[Co(en)3]2+同时吸收去除SO2和NO的影响因素,实验结果表明,pH值和脱硫剂种类是影响乙二胺合钴同时脱除NO和SO2的最重要影响因素,烟气中的氧促进乙二胺合钴吸收NO和SO2,烟气中的SO2,CO2和NO2对乙二胺合钴吸收NO具有抑制作用。在实验条件温度为20℃,pH为13.0,[Co(en)3]2+浓度为0.025 mol/L,加入1 g NH3.H2O的脱硝率更好,连续吸收60 min,脱硝率均保持在93.5%,加入NaOH和NH3.H2O的脱硫效果最好。乙二胺合钴络合同时脱除NO和SO2完全可以在一个装置中完成。     

The MAGIC simulation of surface water acidification at, and first year results from, the Bear Brook Watershed Manipulation, Maine, USA

The catchments of East and West Bear Brooks, Maine, USA, have been hydrologically and chemically monitored for 3.5 years. Stream chemistries and hydrographs are similar. These clear water streams are low in ANC (0-70 microeq litre(-1)), with variations caused by changing concentrations of base cations, SO4, NO3 and Cl. The latter range between 90-120, 0-40 and 65-75 microeq litre(-1), respectively. The West Bear catchment is being treated with six applications per year of dry (NH4)2SO4 at 1800 eq ha(-1) year(-1). After one year of treatment, the response of the stream chemistry and the response modelled by MAGIC are similar. Retentions of NH4 and SO4 are nearly 100% and greater than 80%, respectively. The additional flux of SO4 is compensated principally by an increased Ca concentration. Episodes of high discharge in the treated catchment are now characterized by lower ANC and pH, and higher Al than prior to the manipulation. Concentrations of NO3 have increased about 10 microeq litre(-1) during the dormant season, presumably due to additional nitrification of N from NH4. Discharge-chemistry relationships indicate that changes in stream chemistry, except for NO3, are dominated by ion exchange reactions in the upper part of the soil profile.     

沸石负载淀粉对Pb2＋、Cu2＋和Ni2＋的吸附性能

将淀粉负载到沸石表面得到新型重金属离子复合吸附剂ZLS。分别从沸石与淀粉质量比、吸附温度、吸附时间、pH与重金属初始浓度不同方面考察了复合吸附剂ZLS吸附Pb^2＋、Cu^2＋、Ni^2＋的影响。实验结果表明：当沸石与淀粉质量比为10：1,pH为6,吸附温度在30℃时,复合型吸附剂ZLS对Pb^2＋、Cu^2＋和Ni^2＋3种重金属离子的吸附效果最好;吸附动力学研究发现,ZLS对Pb^2＋、Cu^2＋和Ni^2＋的吸附行为均符合准二级动力学以及颗粒内部扩散模型;等温吸附数据符合Fre-undlich模型,吸附状态属于多层吸附。     

Adsorption characteristics of Ni(II) on gamma-type alumina particles and its determination of overall adsorption rate by a differential bed reactor

The adsorption experiment of nickel ion [Ni(II)] on gamma-type alumina by a differential bed reactor in aqueous solutions was investigated to determine the adsorption characteristics and overall adsorption rate. The adsorbed amount increased rapidly with pH from pH 2 to 6 and kept constant over pH 6. The adsorbed amount of Ni(II) increased with temperature from 20 to 50 degrees C. Correlation coefficients (R2) of Langmuir and Freundlich adsorption isotherms were 0.9268 and 0.9489, respectively, and Freundlich isotherm was more suitable for adsorption on gamma-type alumina than Langmuir isotherm.The overall adsorption rate of Ni(II) on gamma-type alumina at pH 6 by a differential bed rector was determined as follows: r = 68.77Ce(1.61) - 17.60qe(0.36). Al(III) ions in solutions were away from the alumina surface during the adsorption of Ni(II) and Al(III) concentration increased with an increasing Ni(II) adsorbed amount on alumina.