Aluminium speciation in effluents and receiving waters

The respective speciation of aluminium in sewage effluent and in river water receiving effluent, has been examined. Results showed that concentrations of reactive aluminium changed over a timescale of hours and were controlled predominantly by pH. A minimum concentration of reactive aluminium occurred at a pH of approximately 6.8, coinciding with the prevalence of non-reactive, insoluble Al(OH)3 species. For receiving waters of low pH value, typically < pH 5, a large proportion of the 'naturally present' aluminium can be present in a reactive form at concentrations higher than the proposed Environmental Quality Standard (EQS). Mixing of waters of this type with effluent of a higher pH value leads to the precipitation of aluminium hydroxide. Mixing of effluent of pH value in the range 7.5-8.0 with river water in the same (or slightly higher) pH range appears to result in no appreciable change in the proportion of reactive aluminium; the change in concentration tends to be related simply to dilution. On the basis of a theoretical knowledge of aluminium speciation, results obtained in this work indicate that it is possible to make predictions about the proportion of reactive aluminium present in a receiving water, based on the pH values of the effluent water mixture and the concentration in the effluent. Reasonable comparisons between measured and predicted values were obtained at higher pH values, but the relationship was less certain at pH values less than 6.5 for which levels of reactive metal tended to be higher than the quality standard value.     

Towards the establishment of an environmental quality standard for aluminium in surface waters

Steps taken to establish an environmental quality standard (EQS) for aluminium are described. The range of water types in England and Wales and the concentrations of low molecular weight (active) forms of aluminium have been assessed in order to evaluate the risk posed by aluminium in surface waters. Levels of low molecular weight forms of aluminium are mainly in the range 0-25 microg l(-1). Data suggest that dissolved aluminium might form the basis of a reasonably useful prediction of active aluminium leading to a simplified approach to compliance monitoring of an EQS set in terms of active aluminium.     

The application of ICP-SMS, GF-AAS and HG-AFS to the analysis of water and sediment samples from a temperate stratified estuary

Three atomic spectrometry techniques, namely sector field inductively coupled plasma mass spectroscopy, graphite furnace atomic absorption spectrometry and hydride generation atomic fluorescence spectroscopy (ICP-SMS, GF-AAS and HG-AFS, respectively), housed at separate independent laboratories, were used to analyse water and sediment samples collected from the Huon River Estuary, SE Tasmania (Australia) in the Austral spring 1998. A dithiocarbamate-chelation/back-extraction technique was used to separate and preconcentrate Co, Ni, Cu, Zn, Cd and Pb from eight collected water samples prior to analysis by ICP-SMS and GF-AAS. A number of other elements in the waters were analysed directly (Mn, Fe and Zn by GF-AAS; As by HG-AFS), or following sample dilution (1 + 19: V, Mn, Fe, As, Mo, Ba and U by ICP-SMS). Where possible, previously corroborated GF-AAS and HG-AFS techniques were used to verify obtained ICP-SMS results. From the analysis of four reference waters (SLEW-1 and -2, SLRS-3 and NASS-5), good agreement, to within +/- 10-20%, was typically found between certified (or information only values) and measured results (irrespective of analytical technique). Exceptions included Zn (and sometimes Fe) that could not be quantified by ICP-SMS due to elevated blank signals, and As which was found to lie below ICP-SMS detection limits. For Huon Estuary water samples, inter-method agreement was within +/- 10-20% (for those elements amenable to analysis by more than one technique). Nitric acid extracts of two certified reference materials (Buffalo River Sediment and BCSS-1) and six Huon Estuary sediments were analysed by ICP-SMS (for Al, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Cd and Pb) and HG-AFS (for As). Results from the certified reference materials indicated extraction efficiencies of 60 70% (for most elements). A close correlation between ICP-SMS and HG-AFS was obtained for leachable As in the sediments. In terms of potential inorganic contaminants, the Huon Estuary was found to be a relatively 'clean' water system. The elemental concentrations measured in water and sediment samples from this region were found to lie within current Australian guidelines for estuaries. In general, no one analytical technique was able to accurately determine all elements in all samples from this relatively pristine estuarine environment. A combination of all three analytical techniques was necessary for the successful analysis of the elements considered in this study.     

The role of size exclusion chromatography-flame atomic absorption spectrometry in the treatment chemistry of potable water

The percentage composition of Al13, [AlO4Al12(OH)24(H2O)12]7+, in water treatment coagulants is an important criterion in the development and use of polymeric coagulants. Polymeric coagulants are generally used in cold climates or with highly turbid waters. Size exclusion chromatography flame atomic absorption spectrometry (SEC-FAAS) can separate Al13 and monomeric Al within 6 min. The percentage composition of Al13 and monomeric Al is determined by solving two simultaneous equations. Due to overlapping peaks, a 10% error is associated with this method of quantification. This method can be used on coagulants of varying "r values" (r=[OH-]/[Al3+]), or on mixtures of those coagulants and monomeric aluminium.     

Solid phase extraction of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) ions with 1-(2-thiazolylazo)-2-naphthol loaded Amberlite XAD-1180

A new method for separation and preconcentration of trace amounts of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) ions in various matrices was proposed. The method is based on the adsorption and chelation of the metal ions on a column containing Amberlite XAD-1180 resin impregnated with 1-(2-thiazolylazo)-2-naphthol (TAN) reagent prior to their determination by flame atomic absorption spectrometry (FAAS). The effect of pH, type, concentration and volume of eluent, sample volume, flow rates of sample and elution solutions, and interfering ions have been investigated. The optimum pH for simultaneous retention of all the metal ions was 9. Eluent for quantitative elution was 20 ml of 2 mol l(-1) HNO(3). The optimum sample and eluent flow rates were found as 4 ml min(-1), and also sample volume was 500 ml, except for Mn (87% recovery). The sorption capacity of the resin was found to be 0.77, 0.41, 0.57, and 0.30 mg g(-1) for Cu(II), Ni(II), Cd(II), and Mn(II), respectively. The preconcentration factor of the method was 200 for Cu(II), 150 for Pb(II), 100 for Cd(II) and Ni(II), and 50 for Mn(II). The recovery values for all of the metal ions were > or = 95% and relative standard deviations (RSDs) were < or = 5.1%. The detection limit values were in the range of 0.03 and 1.19 microg l(-1). The accuracy of the method was confirmed by analysing the certified reference materials (TMDA 54.4 fortified lake water and GBW 07605 tea samples) and the recovery studies. This procedure was applied to the determination of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) in waste water and lake water samples.     

Determination of trace transition metals in environmental matrices by chelation ion chromatography

Trace transition metals (Fe^3?+?, Mn, Cu, Cd, Co, Zn, Ni) in environmental samples were analyzed by chelation ion chromatography using a mixed bed ion-exchange column with pyridine-2,6-dicarboxylic acid (PDCA) and oxalic acid as eluent and large volume direct injection (1,000 ??l). The two eluents, PDCA and oxalic acid, were tested, and repeatability and detection limits were compared. The total analysis time was ~15 min. The separation with PDCA was more successful than that obtained with acid oxalic. It was observed that utilizing PDCA resulted in lower detection limits, higher repeatability, and a quantitative detection of Cd and Mn, which coelute as a single peak when using the oxalic acid. At last, the PDCA calibration graphs resulted linear (r ²?>?0.999) in the range 0.4?C1,000 ??g/L. The procedure was applied to the analysis of metals in soils and in water samples. The results obtained from the analysis of natural waters have demonstrated that the method is simple and efficient, therefore, can be used for the determination of metals in natural waters using a continuous and automatic monitoring system.     

Application of natural zeolites for preconcentration of arsenic species in water samples

Zeolites of the clinoptilolite type produced in Mexico and Hungary were investigated with respect to their sorption efficiency for various redox species of arsenic. Long-term experiments showed that arsenate remains stable for a long period in spiked deionised water and drinking water, as well as in the surface water of the Biela valley in Saxony, Germany. Both clinoptilolites are able to decrease the initial arsenic concentration of 200 microg l(-1) by more than 75% in deionised, drinking, ground and surface waters. In the case of the Mexican zeolite, both the arsenite and the arsenate concentrations (200 microg l(-1)) can be lowered from 200 microg l(-1) to 10 microg l(-1), which is the World Health Organisation's (WHO's) recommended maximum level. It was found that the presence of cations and anions in the natural waters of Biela, Germany, and Zimapán, Mexico, did not reduce the efficiency of the selected zeolites. The Hungarian zeolite removed 75% of the arsenate in the Zimapán water and only 50% when the sample was first acidified. This zeolite totally desorbed the fixed arsenic into a water volume that was half the volume in the adsorption experiment.     

Solid phase extraction of gold(III) on silica gel modified with benzoylthiourea prior to its determination by flame atomic absorption spectrometry

A new method has been developed for the determination of gold based on separation and preconcentration using silica gel modified with benzoylthiourea. The optimum experimental parameters for preconcentration of gold, such as acid concentration, sample flow rate, eluent and matrix ions, have been investigated. Gold could be quantitatively retained in the 0.25-2.0 mol L(-1) HCl and HNO(3) concentrations, and then eluted completely with 0.5 mol L(-1) thiourea in 1.0 mol L(-1) HCl. The sorption capacity of gold(III) is 0.92 +/- 0.04 mmol g(-1) with a high enrichment factor of 267. The relative standard deviation of the method, RSD%, was found as 1.2% for 0.1 microg mL(-1). The detection limit for gold was 1.4 microg L(-1). The validation of the proposed method was checked by the analysis of certified reference soil materials. The presented procedure was applied to the determination of gold in some environmental samples.     

Element content of propolis collected from different areas of South Spain

The aim of this work is to determine the content of essential and toxic elements in 25 raw propolis samples, when considering pollution agents and geographical and botanical factors. The microwave-assisted digestion was the most reliable and accurate method for determination of inorganic elements in propolis samples. The results were obtained using certified reference materials in a good agreement with certified values. Inductively coupled plasma atomic emission spectroscopy was used for the determination of 23 macro- and microelements (Ag, Al, As, B, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, and Zn). A Mercury analyzer was also utilized for the detection of the total Hg. Among the analyzed metals, Ca, K, Mg, Zn, Si, S, Fe, Al, P, and Na were found to be the most predominant. Heavy metals (As, Cd, Hg, and Pb) were determined in minimal concentration, and Pb was the highest mean contained toxic (<3.80 mg/kg), without influence on provisional tolerable weekly intake values. The method can be applied for routine analysis and quality and environmental pollution controls of toxic elements in propolis samples. The results obtained indicate no pollution of the collection areas and naturally high concentration of Al (460?±?62.2 mg/kg).     

Contamination from historic metal mines and the need for non-invasive remediation techniques: a case study from Southwest England

The UK is legally required by the EU Water Framework Directive (WFD) to improve the environmental quality of inland and coastal waters in the coming years. Historic metal mine sites are recognised as an important source of some of the elements on the WFD priority chemicals list. Despite their contamination potential, such sites are valued for their heritage and for other cultural and scientific reasons. Remediating historic mining areas to control the contamination of stream waters, whilst also preserving the integrity of the mine site, is a challenge but might be achieved by novel forms of remediation. In this study, we have carried out environmental monitoring at a historic, and culturally-sensitive, lead-silver mine site in southwest England and have undertaken a pilot experiment to investigate the potential for a novel, non-invasive remediation method at the site. Concentrations of Pb and Zn in mine spoil were clearly elevated with geometric mean concentrations of 6,888 and 710 microg g(-1), respectively. Mean concentrations of Pb in stream waters were between 21 and 54 microg l(-1), in exceedance of the WFD environmental quality standard (EQS) of 7.2 microg l(-1) (annual average). Mean Zn concentrations in water were between 30 and 97 microg l(-1), compared to the UK EQS of 66.5 microg l(-1) (average). Stream sediments within, and downstream from, the mining site were similarly elevated, indicating transport of mine waste particles into and within the stream. We undertook a simple trial to investigate the potential of hydroxyapatite, in the form of bonemeal, to passively remove the Pb and Zn, from the stream waters. After percolating through bonemeal in a leaching column, 96-99% of the dissolved Pb and Zn in stream water samples was removed.     

线性扫描溶出伏安法同时测定水样中铅镉铜锌

通过多壁碳纳米管-Nafion复合膜修饰电极,建立水样中痕量铅、镉、铜、锌同时测定的线性扫描溶出伏安分析法,优化支持电解质及pH值、修饰剂用量、富集电位及时间等测定条件。实验结果表明,在pH 4.0的NaAc-HAc缓冲液中,-1.20V富集5min后,在电位-1.04V、-0.72V、-0.45V及-0.16V附近分别产生锌、镉、铅、铜的灵敏溶出峰,测定各元素的线性关系良好,相对标准偏差均小于5.4%。该法已成功应用于实际水样中痕量铅、镉、铜、锌的同时测定,加标回收率在93.3%~106.7%之间,结果满意。     

高效液相色谱法直接测定环境水体中直链烷基苯磺酸钠类阴离子表面活性剂

使用亚甲蓝分光光度法和流动注射法分析环境水体中的阴离子表面活性剂的过程中用到的三氯甲烷会带来次生环境污染问题,同时也会在一定程度上影响检测人员的健康。结合现有仪器设备,通过优化检测流程,建立了一种适用于高海拔条件下测定环境水体中直链烷基苯磺酸钠(LAS)类阴离子表面活性剂的方法。该方法以十二烷基苯磺酸钠(SDBS)为定量标准物质,采用高效液相色谱法测定,使用归一化法定量。经验证,在0.02~2.00 mg/L浓度范围内,所建立校准曲线的线性回归系数在0.999以上。该方法具有良好的检出能力(检出限为0.01 mg/L)和抗干扰能力,重复性范围为1.3%~6.2%,准确度范围为2.1%~4.0%,回收率范围为80.0%~116%,相关验证参数均能满足实际样品的分析要求。检测过程避免了二次污染物的产生,减少了对实验人员健康的影响。该方法具有操作简便、高效且对环境友好的特点。     

A biomaterial based approach for arsenic removal from water

We demonstrate that the non-living, dried roots of the water hyacinth plant [Eichhornia crassipes(Mart.) Solms] can rapidly remove arsenic from water. Atomic absorption spectrometry was used to demonstrate that more than 93% of arsenite (As(iii)) and 95% of arsenate (As(v)) were removed from a solution containing 200 microg As l(-1) within 60 minutes of exposure to a powder produced from dried roots. No difference in removal efficiency was observed between the two oxidation states of As studied. The amount of arsenic remaining in solution was found to be less than 10 microg l(-1) which is the WHO guideline limit value for As in drinking water. The presence of arsenic in drinking water in a number of countries in the developing world has been found to be much higher than the WHO level, affecting the health of millions of people. In this paper, we show that a biomaterial produced from dried water hyacinth roots, a plant that is found in abundant supply in many parts of the world, can provide a simple, effective and yet cheap method for removing arsenic from contaminated water.     

Aluminium concentrations in Swedish forest streams and co-variations with catchment characteristics

The negative effects of elevated concentrations of inorganic aluminium on aquatic organisms are well documented. Acid deposition is often cited as a main driver behind the mobilisation and speciation of aluminium in soils and surface waters. In the study, we tested the hypothesis that sulphur deposition is the main driver for elevated concentrations of inorganic aluminium in 114 base poor, boreal Swedish streams. However, the deposition of anthropogenic sulphate has decreased substantially since it peaked in the 1970s, and at the current deposition levels, we hypothesise that local site parameters play an important role in determining vulnerability to elevated concentrations of inorganic aluminium in boreal stream waters. Presented here are the results of a principal components analysis of stream water chemistry, acid deposition data and local site variables, including forest composition and stem volume. It is shown that the concentrations of both organic and inorganic aluminium are not explained by either historical or current acid deposition, but are instead explained by a combination of local site characteristics. Sites with elevated concentrations of inorganic aluminium were characterised by small catchments (<500 ha) dominated by mature stands of Norway spruce with high stem volume. Using data from the Swedish National Forest Inventory the area of productive forest land in Sweden with a higher vulnerability for elevated inorganic aluminium concentrations in forests streams is approximately 1.5 million hectares or 7% of the total productive forest area; this is higher in the south of Sweden (10%) and lower in the north (2%). A better understanding of the effects of natural processes and forest management in controlling aquatic inorganic aluminium concentrations is therefore important in future discussions about measures against surface water acidification.     

Investigation of sequential and enzymatic extraction of arsenic from drinking water distribution solids using ICP-MS

A sequential extraction approach was utilized to estimate the distribution of arsenite [As(iii)] and arsenate [As(v)] on iron oxide/hydroxide solids obtained from drinking water distribution systems. The arsenic (As) associated with these solids can be segregated into three operationally defined categories (exchangeable, amorphous and crystalline) according to the sequential extraction literature. The exchangeable As, for the six drinking water solids evaluated, was estimated using 10 mM MgCl(2) and 10 mM NaH(2)PO(4) and represented between 5-34% of the total As available from the solid. The amorphously bound As was estimated using 10 mM (NH(4))(2)C(2)O(4) and represented between 57-124% of the As available from the respective solid. Finally, the crystalline bound As was estimated using titanium citrate and this represented less than 1.5% of the As associated with the solids. A synthetic stomach/intestine extraction approach was also applied to the distribution solids. The stomach fluid was found to extract between 0.5-33.3 microg g(-1) As and 120-2,360 microg g(-1) iron (Fe). The As concentrations in the intestine fluid were between 0.02-0.04 microg g(-1) while the Fe concentration ranged from 0.06-0.7 microg g(-1) for the first six drinking water distribution solids. The elevated Fe levels associated with the stomach fluid were found to produce Fe based precipitates when the intestinal treatment was applied. Preliminary observations indicate that most of the aqueous Fe in the stomach fluid is ferric ion and the observed precipitate produced in the intestine fluid is consistent with the decreased solubility of ferric ion at the pH associated with the intestine.     

2-Nitroso-1-naphthol as a selective reagent for preconcentration of cobalt by vortex assisted combined with solidification of organic droplet and its determination by flame atomic absorption spectrometry

Highly rapid and selective vortex-assisted liquid–liquid microextraction based on solidification of organic drop has been used for determination of cobalt ion. 2-Nitroso-1-naphthol (2N1N) was used as a selective complexing agent to form stable cobalt–2N1N complex which can be extracted with 1-undecanol at a short time by the assistance of vortex agitator system followed by its determination using flame atomic absorption spectrometry. In vortex assisted, vigorous vortex stream as well as the vibrant effect of vortex system cause very fine droplets of extraction solvent to be produced and extraction occurred at a short time. Some parameters influencing the extraction process such as pH of samples, concentration of 2-nitroso-1-naphthol, extraction solvent volume, extraction time, ionic strength and surfactant addition, as well as interferences were evaluated in detail and optimum conditions were selected. At the optimum conditions, the calibration curve was linear in the range of 15 to 400 μg L^?1 of cobalt ions. The relative standard deviation based on ten replicate analysis of sample solution containing 50 μg L^?1 of cobalt was 3.4 %. The detection limit (calculated as the concentration equivalent to three times of the standard deviation of the blank divided by the slope of the calibration curve after preconcentration) was 5.4 μg L^?1. The accuracy of the proposed method was successfully evaluated by the analysis of certified reference materials. This selective and highly rapid method was used for determination of cobalt ions in different water samples.     

Spatio-temporal variations of organic carbon and chlorophyll degradation products in the surficial sediments of Izmir Bay (Aegean Sea/Turkey)

The aim of this research is to determine the effects of Izmir Big Channel Waste Water Treatment Project on the sediment quality of Izmir Bay. Wastewater treatment improves the water quality. However, sediment does not respond to this treatment as fast as water column. Monitoring of bottom water and sediment quality is necessary for identification of the recovery of the whole ecosystem. For this purpose, bottom water and sediment samples were collected from three stations which are located in the middle and inner parts of the Izmir Bay on a monthly basis between January 2003 and December 2003. Values measured at stations ranged between; 0.54-12.82 microg/L for chlorophyll-a, 0.09-9.32 microg/L for phaeopigment, 0.05-1.91 mg/L for particulate organic carbon in bottom waters, 11.88-100.29 microg/g for chlorophyll degradation products and 1.12-5.39% for organic carbon in sediment samples. In conclusion, it was found that grazing activity explained carbon variations in sediment at station 2, but at station 1 and station 3 carbon variations in sediment were not related to autochthonous biological processes.     

A very sensitive flow-injection spectrophotometric determination method for iron (II) and total iron using 2′, 3, 4′, 5, 7-pentahydroxyflavone

In this study, an ultra-sensitive and highly selective, rapid flow-injection spectrophotometric method for the determination of iron (II) and total iron has been proposed. The method was based on the reaction between iron (II) and 2′, 3, 4′, 5, 7-pentahydroxyflavone in slightly acidic solution with a strong absorption at 415 nm. The carrier solution used was 1?×?10^?5 M 2′, 3, 4′, 5, 7-pentahydroxyflavone in 0.1 M HAc/Ac^? buffer solution at pH 4.5. Parameters that affect simultaneously the determination of iron (II) and interfering ions were tested. The relative standard deviation for the determination of 50 μg L^?1 iron (II) was 0.85 % (n?=?10), and the limit of detection (blank signal plus three times the standard deviation of the blank) was 3 μg L^?1, both based on injection volumes of 20 μL. The method has been successfully applied to the determination of iron (II) and total iron in water samples and ore samples. The method was verified by analysing a certified reference material Zn/Al/Cu 43XZ3F.     

测定地表水中悬浮物的空白校正

进行了测定地表水中悬浮物空白校正与不作空白校正的对比试验 ,得出不作空白校正存在较大误差 ,认为测定地表水中悬浮物时应作空白校正。同时用测定海水中悬浮物的方法作测定地表水中悬浮物的试验 ,试验效果较好 ,符合测定要求。建议可用测定海水中悬浮物的方法来测定地表水中悬浮物     

Flow-injection analysis with fluorescence detection for the determination of trace levels of ammonium in seawater

A method using flow-injection, gas-diffusion, derivatisation and then fluorescent detection has been established for ammonium ion determination in seawater. The fluorescent derivative formed by reacting ortho-phthaldialdehyde (OPA) and sulfite with ammonia gives high sensitivity while removing potential interferences. This is required to measure the low concentrations of ammonium often seen in the open ocean. The experimental conditions (flow-rate, reagent concentrations, membrane configurations, etc.) were manipulated to improve performance. For a sample throughput of 30 samples h(-1), the limit of detection was 7 nM, the coefficient of variation was 5.7% at 800 nM, and the calibration curve was linear to at least 4 micromol L(-1). Interferences were minimised by a gaseous diffusion step. Volatile small molecular-weight amines as interferents were discriminated against by this method. They neither passed through the membrane as efficiently as ammonia, nor reacted as readily with OPA when sulfite was the reductant. Contamination by ammonia from laboratory and shipboard sources complicates application of the method to natural waters, especially measurement of low concentrations (<100 nM) in open-ocean waters. Steps to overcome contamination are described in detail. Some results are presented for ammonium determination in Southern Ocean and Huon Estuary (Tasmania) waters.