Aluminium complexation by an aquatic humic fraction under acidic conditions

Equilibrium dialysis and acid-base titration were used to investigate the interactions between Al and a fraction of aquatic humic substances (HS), in the pH range 3–5. Binding of Al by the HS increased with Al³⁺ activity and with pH. Under conditions relevant to natural waters, υ (mol Al bound per gHS) varied from 0 to 1.5 × 10⁻³. The data were modelled with an emprical linear logarithmic expression (Model I) and on the basis of the polyelectrolyte nature of the HS, incorporating competitive binding of H⁺ and Al³⁺ (Model II). Both models gave tolerable fits (r = 0.93). Model I is simpler to apply, while Model II allows the calculation of proton release accompanying Al binding, and provides information on the net charge of the Al---HS complexes. The results were used to calculate the distribution of Al between organic and inorganic forms under conditions prevailing in acidic natural waters.     

The complexation of protons, aluminium and calcium by aquatic humic substances: A model incorporating binding-site heterogeneity and macroionic effects

A model is presented that describes the competitive binding of protons and metal ions (Al³⁺, AlOH²⁺, Ca²⁺) by humic substances (HS) in the pH range 3–6 and at different ionic strengths, and allows the net humic charge to be calculated. The HS are treated in terms of two types of carboxyl group, together with other more weakly-acidic groups, and the influence of humic (macroionic) charge is taken into account. Eight parameters are involved: total humic acidity, which can be measured directly, content of COOH groups, 4 intrinsic equilibrium constants (2 for H⁺ binding, 2 for metal binding), and 2 parameters accounting for charge effects at different ionic strengths. The model was applied to 4 aquatic humic samples, parameters being estimated from acid-base titration data. The equilibrium contents did not vary greatly among the humic samples, which is consistent with the idea that the functional groups in each sample are chemically the same. The effect of humic charge on complexation varies considerably among the samples. The model was reasonably successful at predicting humic-bound Al in laboratory-prepared solutions and field samples. Calculations based on the model suggest that, (1) Ca²⁺ does not compete significantly with Al for binding to HS under natural acid conditions, and (2) that there is a direct relationship between humic solubility and net humic charge.     

Optimising natural organic matter removal from low turbidity waters by controlled pH adjustment of aluminium coagulation

Effective removal of soluble natural organic matter (NOM) from low-turbidity waters can be achieved by aluminium coagulation provided due attention is paid to micro-floc formation (coagulation) and macro-floc development (flocculation). This work provides guidelines and an explanation of how pH should be controlled to maximise soluble NOM removal while at the same time making full use of pH-influencing chemicals (acid, alum, and lime). For low-turbidity waters, essential floc nucleating sites can be provided by the lime that is used for pH and alkalinity adjustment, provided that the lime is added in sufficient quantity and at a point where it retains some of its particulate nature, i.e. immediately after coagulant addition. Adjusting the pH downwards to between 4 and 5 prior to coagulant addition allows the formation of soluble NOM-aluminium complexes that link to each other, thereby forming large insoluble bridged complexes (micro-flocs), that also act as nuclei for macro-floc development (flocculation).     

Combined use of calcium salts and polymeric aluminium hydroxide for defluoridation of waste waters

The combined use of calcium salt and polymeric aluminium hydroxide, P, for treatment of fluoridated waste water has been described. In the proposed method of treatment the calcium ions acts as the precipitant and polymeric aluminium hydroxide as the coagulant. At low fluoride concentrations (2 × 10⁻³ M) the precipitation reaction of calcium fluoride is a slow process. The residual fluoride concentrations found experimentally approached the theoretically predicted values only at high calcium concentrations (| F | _t/ | Ca | _I molar ratio = 0.24) and for long equilibration times. The addition of calcium fluoride seeds (approx. 20 mg 1⁻¹) accelerated the precipitation process and the results obtained for the residual fluoride concentrations were close to the theoretically calculated ones regardless of the calcium ion concentration used. Under these conditions fine CaF₂ precipitate with poor settleability was formed. The addition of small amounts of polymeric aluminium hydroxide, P, (F/Al molar ratio = 10) greatly facilitates the settleability of the precipitate. The advantage of using P over alum for the removal of fluoride is that less concentration of the former is required and the reproducibility of the results are good. The effect of sulphate on the precipitation of calcium fluoride has been also studied. Tests with fluoride containing waste water collected from aluminium industry showed that fluoride can be effectively removed.     

An optimal manual procedure for ammonia analysis in natural waters by the indophenol blue method

Several procedures for ammonia determination in natural waters by the colorimetric indophenol blue method were tested. Solórzano's procedure, with phenol-alcohol, nitroprusside, alkaline citrate and hypochlorite as reagents, was shown to be appropriate for routine work. An improvement of this procedure was obtained by replacing hypochlorite with sodium dichloro-iso-cyanurate, by adding the catalyst after all other reagents, and by increasing the working pH. Concentration factors are statistically the same as in the original procedure, but the reagent blanks are lower and the color develops faster, both in fresh and in sea water.     

Limestone neutralization of acid waters in the presence of surface precipitates

Acid waste waters are usually treated by means of lime in order to meet pH requirements for discharge. Considerable saving may be achieved using limestone in neutralization processes.The feasibility of limestone neutralization processes also in those cases where precipitates form both on the reactive surface and in the liquid bulk as pH rises has been evaluated.Experiments were carried out with a well mixed tank reactor contacting limestone with acid solutions containing iron (III) sulphate and sulphuric acid. Analyses for calcium and iron (III) concentrations as well as for CO₂ desorption rate for their changes with time and continuous recording of pH were carried out during each run.The results show that neutrality can be achieved within a few minutes providing the operation conditions ensure a continuous removal of precipitates from the reacting surface.A critical comparison with previous results concerning a similar system containing AlCl₃ and HCl emphasizes the phenomenological differences between the two systems.The kinetic model for limestone dissolution in acid solutions previously developed has been successfully applied to the system studied.     

The effect of surface active substances on the electrochemical behaviour of copper ions in chloride solutions and in natural waters

Electrochemical methods have been used in the study of the adsorption behaviour of different surface active substances, biogenic and non-biogenic, as well as in the study of their complexation properties for copper ions in chloride solutions and in natural waters. The influence on the anodic oxidation wave of copper has been examined.

For surface active substances (humic substances and proteins), which at the same time exhibit complexation properties towards copper ions, the main interaction will be complexation, especially in the lower concentration range of both copper and the organic substance. At higher concentrations of the surface active substances and copper ions adsorption effects may play a role in oxido-reduction processes of copper at the electrode surface covered with organic coating.

Contrary to cadmium, the electrode reaction of copper is not greatly influenced by synthetic surface active substances like Triton X-100 and sodium dodecylsulphate, since in the potential range of the anodic wave of copper most synthetic surface actice substances are desorbed from the mercury electrode surface.

In natural samples the main interaction will be complexation of copper ions with the organic matter. Investigations of the interfacial interactions between copper and organic coatings have to be continued on the other surfaces, natural and/or model ones, which have different surface properties and will be of greater environmental significance. Mercury electrode/solution interface is not a very convenient model for the study or interfacial interactions of copper ions because of the nature of the electrode process of copper.     

Determination of soluble aluminium concentration in alkaline humic water using atomic absorption spectrophotometry

The steps of the standard method to determine soluble aluminium concentration are filtering, followed by acidifying, then analysing with the atomic absorption spectrophotometer (AAS). When applied to alkaline humic water, acidification gives rise to the formation of humic acid as a brown particulate matter. Of the total soluble aluminium in the original water, 49-61% forms complexes with the particulate humic acid upon acidification. Although the AAS is capable of detecting the binding aluminium, the particulate nature of humic acid easily induces inaccurate readings as a result of the non-uniform distribution of the particulate matter. A more precise analysis of soluble aluminium concentration of alkaline humic water is shown to be achievable in basicified solutions instead. Basicified solutions keep humic acid in the soluble form; hence maintain the homogeneity of the sample.     

Fractionation of dissolved organic matter from surface waters using macroporous resins

To obtain fractions enriched with biodegradable dissolved organic carbon (BDOC) or with organic compounds responsible for the chlorine demand (CID) and for trihalomethane formation potential (THMFP), Seine river water samples were percolated on various macroporous resins (anionic, cationic and non-ionic) and compared with granulated activated carbon (GAC). In addition, measurement of UV absorbance at 254 nm and the fluorescence index (λ_excitation 320 nm) had allowed to follow up the retention of dissolved organic matter by the different adsorbants. In contrast to cationic and non-ionic resins, anionic resins confirm their excellent retention capacity of organic compounds responsible for UV 254 absorbance and fluorescence index. The relative values of BDOC/DOC ratio (mg-C/mg-C) are slightly increased in the effluents of anionic resins, indicating that they retain a little preferentially the refractory fraction instead of the biodegradable fraction. There is no significant difference between the ratio of CID/DOC (mg-Cl₂/mg-C) in influent and effluent of anionic resins. Cationic resin has a low capacity for retention of DOC, but they seem to retain significantly the organic compounds responsible for CID. The capability of anionic resins to retain THMFP is similar to that of GAC.     

Degradation of monomethylmercury chloride by hydroxyl radicals in simulated natural waters

The degradation of methylmercury chloride by hydroxyl radicals (*OH) has been investigated using nitrate photolysis from 285 to 800 nm with a 450 W Xenon lamp as the (*OH source. The identified products are Hg(2+), Hg(0), CHCl(3) and formaldehyde. The second-order rate constant at pH of 5 at room temperature was determined to be 9.83(+-0.66)x10(9) M(-1) x s(-1)using benzoic acid as the *OH scavenger. The effects of chloride concentration and methylmercury speciation have also been investigated. A mechanism of the CH(3)HgCl-*OH reaction has been proposed. The calculated methylmercury degradation rates in natural waters using the above rate constant were comparable to the in situ photodegradation rates reported previously, indicating that degradation by (*)OH may be one of the important pathways of methylmercury degradation in sunlit surface waters.     

Aluminium speciation in acidic natural waters: Testing of a model for al-humic complexation

Concentrations of organically-complexed monomeric Al, [Al_m-org], in field samples are compared with those predicted from the equation where [HS] is the concentration of humic substances, curly brackets indicate activities, and α, β and γ are constants. Results for 114 field samples from 8 locations in N.W. Europe and N. America were considered with [Al_m-org] in the range 0–10 μM. Using α, β and γ values derived from the results of laboratory experiments, a satisfactory agreement between measured and predicted values was obtained with a mean residual (measured —calculated value) of −0.2 μM Al, a root mean square (RMS) residual of 0.9 μM Al and r = 0.92. The 95% confidence limits for the estimation of [Al_m-org] correspond to the calculated value ± 1.8 μM. For some sampling locations the RMS residual can be made smaller by using the measured values of [Al_m-org] to rescale α.     

Application of pyrolysis-gas chromatography-mass spectrometry to the characterization of humic substances resulting from decay of aquatic plants in sediments and waters

Pyrolysis-GC-MS, elemental analysis and i.r. spectroscopy reveal major differences between humic substances from aquatic plants (algae and aquatic phanerogams) and lagoonal, marine and lacustrine deposits. Algae are enriched in proteins and their pyrolysis yields numerous nitrogenous by-products (alkylpyrroles, nitriles and alkylpyridines) along with aromatic compounds which are thought to reflect the decomposition of individual amino-acids (styrene, toluene, phenol and p-cresol). These compounds are less abundant in the pyrolysis products of humic substances from phanerogams with increasing amounts of methoxyphenols, characteristics of lignins.In the deposits of the Kerguelen Islands and of a “blue lake” in Greenland, the importance of algal populations is emphasized by pyrolysis products corresponding to nitrogenous and carbohydrate derivatives. Phenols and cresols in the pyrochromatograms of these samples are interpreted as evidence of polypeptides rather that lignin: p-cresol is much more abundant than the other cresols, suggesting the formation of phenols by way of tyrosine.Lagoonal sediments, in contrast, seem typical of intermixed development of algae and phanerogams.Differences between fulvic and humic acids are emphasized by the development of polyphenols and protein derivatives in humic acids compared to polysaccharide derivatives in fulvic acids. Other constituents revealed by PY-GC-MS include N-acetyl aminosugars, phthalates and aliphatic compounds.     

Prediction of the temperature dependence of electrical conductance for river waters

The application of mixed electrolyte theories to the prediction of the electrical conductivity of 14 river-water samples covering a range of ionic strength and temperatures between 5 and 25°C has been evaluated using a new program, CONCAL. Both the Fuoss-Onsager, FO, and Lee-Wheaton, LW, theories produce better agreement between the measured and predicted conductivities for the majority of the samples than the simple product equation. For river waters with a charge imbalance of less than 10%, the prediction of the simple product, FO and LW equations are on average within 11.1, 3.4 and 3.7%, respectively, of the experimental values over the range of temperatures considered. The major error in the predictions of the FO and LW models is associated with the reliability of the chemical analytical data input to CONCAL. The accuracy of the predictions of the models is also discussed in terms of the magnitude and sign of the charge imbalance calculated for each of the samples from the analytical data.Five equations that are available to apply a temperature compensation to conductivity data to predict values at 25°C have been tested over a temperature range of 5–25°C. The best performance is achieved using the modified Walden's product.The relationship between the measured conductivity at 25°C, κ(25), and ionic strength, I, has been calculated to be I = 0.0021 + 0.0148 κ(25) with I in mmol dm⁻³. This observation is discussed by reference to the predicted relationship for simple binary mixtures of NaCl and Ca(HCO₃)₂.     

Toxicity of aluminium in natural waters controlled by type rather than quantity of natural organic matter

Extension of the conditions under which Al toxicity is tested is required. Environmentally representative preparation of waters is used in investigating roles of alginate (AA) and humic acids (HA) in partitioning of Al (0.5 mg L^− 1), subsequent uptake and accumulation by and toxicity to Lymnaea stagnalis. HA and AA did not alter precipitation of Al(OH)₃, but altered subsequent behaviour of Al. High (40 mg L^− 1) HA concentrations, and to a lesser extent AA, prevented settling and availability for benthic grazing but made deposited Al more likely to be ingested. HA detoxified but AA increased toxicity relative to Al alone. Low concentration (4 mg L^− 1) AA and HA do not change partitioning but increase uptake; they both detoxify, but AA less than HA. The study shows OC:Al ratio is critical in predicting Al behaviour in natural waters, also uptake is mediated by snail behaviour, not solely a function of concentration and form of Al. Therefore, predicting Al behaviour will be subject to errors in determining relevant water composition and response of biota to the new speciation. However, with respect to toxicity, rather than other aspects of Al behaviour, different ratios of HA and Al are insignificant compared to whether AA is present rather than HA.     

The effect of humic acids on the cytotoxicity of silver nanoparticles to a natural aquatic bacterial assemblage

The effect of a terrestrial humic acid (HA) and a river HA on the cytotoxicity of silver nanoparticles (AgNPs) to natural aquatic bacterial assemblages (0 μM, 2.5 μM and 5 μM) was measured with spread plate counting. The effect of HA (20 and 40 ppm) on the cytotoxicity of AgNPs ranging in size between 15 and 25 nm was tested in the presence and in the absence of natural sunlight. The experiment was a full factorial, completely randomized design and the results were analyzed using the General Linear Model in SAS. LSMEANS was used to separate the means or combinations of means. Significant main effects of all independent variables, plus interaction effects in all cases except HA/LI and HA/AgNPs/LI were observed. The toxicity of AgNPs to natural aquatic bacterial assemblages appears to be concentration dependent for concentrations between 0 μM and 5 μM. The data indicate that the light exposure inhibited viability more than the darkness exposure. The HA treatment groups in the presence of light showed greater reduced viability count compared to darkness exposure groups. The inhibition of bacterial viability counts by AgNPs exposure was less in the light treatment groups containing a terrestrial HA compared to that with a river HA. Difference in the extent of reactive oxygen species formation and adsorption/binding of AgNPs was speculated to account for the observed phenomenon.     

Impacts of water quality on chlorine and chlorine dioxide efficacy in natural waters

The impact of disinfection efficacy in natural waters was evaluated by performing disinfection assays using four untreated surface waters of various qualities and ultra-pure buffered waters as a baseline condition for comparison. Bacillus subtilis spores were spiked in these waters and disinfection assays were conducted at 22 degrees C using either free chlorine or chlorine dioxide. Assays using indigenous aerobic spores were also completed. The inactivation kinetics in natural and ultra-pure buffered waters were not statistically different (at p = 0.05) while using free chlorine, as long as disinfectant decay was taken into account. Filtering natural waters through a 0.45 microm did not improve the sporicidal efficacy of chlorine. For three out of the four waters tested, the efficacy of chlorine dioxide was greater in natural waters compared to that observed in ultra-pure buffered waters. Such results are consistent with previous observations using ultra-pure waters supplemented with NOM-extract from the Suwannee River. Similar to free chlorine results, the impact of filtration (0.45 microm) on the efficacy of chlorine dioxide was not statistically significant.     

Effects of natural and synthetic surface active substances on the electrochemical reduction of cadmium in natural waters

Effects of surface active substances, natural and synthetic, in selected samples of seawater, river water and industrial effluents on the oxidation-reduction processes of cadmium have been studied by electrochemical methods and compared with the behaviour of different model compounds.Kinetic parameters, transfer coefficient α and apparent standard rate constant of the cadmium electrode reaction have been estimated from the shape and the height of the corresponding differential pulse voltammograms using theoretical curves obtained by digital simulation of the electrode process. The measure of the inhibition effect of surface active substances on the electrode reaction of cadmium was expressed in terms of the ratio of the rate constants determined in the presence and in the absence of surface active substances.It was found that the degree of inhibition depends on the concentration and type of surface active substances and on the pH of solution.     

混凝和活性炭联用对有机物质的去除效果

研究了混凝和粉末活性炭对水中腐殖酸和苯酚的去除效果,选用聚合氯化铝作为混凝剂和粉末活性炭分别和联合使用时对水中腐殖酸和苯酚的去除效果进行了考察,结果表明：单独使用聚合氯化铝对苯酚的去除效果不佳,先投加活性炭后投加聚合氯化铝比两种同时投加时效果更好。     

Adsorption of trace metals on aluminium oxide: A simulation of processes in freshwater systems by close approximation to natural conditions

The interaction of the trace metals Cu, Co, Zn, Ni, Pb and Cd with aluminium hydroxide precipitated in-situ from homogeneous solution was studied. Using total concentrations of 10⁻⁴ M Al, 10⁻⁷ M Zn, Cu, Co, Ni and 10⁻⁸ M Pb and Cd a removal of Zn, Cu, Pb, Cd from solution occurred together with Al, while Co and Ni concentrations in solution remained unchanged. The binding of Cu, Pb and Zn, Cd is in agreement with the effect predicted by using published (resp. evaluated for Zn and Cd), values for stability constants of surface complexes on preformed Al₂O₃-suspension. The different behaviour of these elements and of Co and Ni is expected from the hydrolysis and adsorption tendencies. The experimental conditions correspond to natural conditions in lake waters, where due to the pH-dependent solubility of aluminium hydroxide, in-situ precipitation may occur and cause the scavenging of trace elements.     

Oxidation of chlorfenvinphos in ultrapure and natural waters by ozonation and photochemical processes

The chemical oxidation of the organophosphorus insecticide chlorfenvinphos, a priority pollutant in aquatic environments, has been conducted in ultrapure water, by means of single degradation agents (ozone and UV radiation), and by the Advanced Oxidation Processes constituted by combinations of these oxidants (O(3)/H(2)O(2) and UV/H(2)O(2)). The influence of the operating variables was discussed, and the degradation rates were evaluated by determining the rate constants for the reactions with ozone ( [Formula: see text] =3.7+/-0.2 L mol(-1)s(-1)) and OH radicals (k(OH)=(3.2+/-0.2)x10(9) L mol(-1)s(-1)), as well as the quantum yield for the photodegradation (around 0.1 mol E(-1), depending on the pH). Additionally, the ozonation of chlorfenvinphos in a natural water system (a surface water from a reservoir) was studied. The influence of the operating conditions on the insecticide removal efficiency was established, and the R(ct) parameter was evaluated. A kinetic model was proposed for the prediction of the elimination rate of chlorfenvinphos in the ozonation process and the results obtained reveal a good agreement between experimental results and predicted values.