Copper(II) complexation by humic and fulvic acids from pig slurry and amended and non-amended soils

The effect of the consecutive annual additions of pig slurry at rates of 0 (control), 90 and 150 m3 ha(-1) y(-1) over a 4-year period on the binding affinity for Cu(II) of soil humic acids (HAs) and fulvic acids (FAs) was investigated in a field plot experiment under semiarid conditions. A ligand potentiometric titration method and a single site model were used for determining the Cu(II) complexing capacities and the stability constants of Cu(II) complexes of HAs and FAs isolated from pig slurry and control and amended soils. The HAs complexing capacities and stability constants were larger than those of the corresponding FA fractions. With respect to the control soil HA, pig-slurry HA was characterized by a much smaller binding capacity and stability constant. Amendment with pig slurry decreased the binding affinity of soil HAs. Similar to the corresponding HAs, the binding affinity of pig-slurry FA was much smaller while that of amended-soil FAs were slightly smaller when compared to the control soil FA. The latter effect was, however, more evident with increasing the amount of pig slurry applied to soil per year and the number of years of pig slurry application.     

Influence of toxicity and dissipation of racemic fenoxaprop and its R-enantiomer in Scenedesmus obliquus suspension by cyclodextrins

Cyclodextrins (CDs), a class of cyclic oligosaccharide molecules containing a variety of chiral centre, are capable of recognizing enantiomeric molecules through the formation of inclusion complexes. In this work, we selected three types of CDs, beta-CD and its two derivatives, randomly methylated beta-CD (RAMEB) and hydroxypropyl beta-CD (HP-beta-CD), to evaluate effects on toxicity of racemic fenoxaprop (rac-FA) and its R-enantiomer (R-FA) to freshwater alga Scenedesmus obliquus (S. obliquus) and their dissipation in S. obliquus suspension with and without CDs addition, respectively, in an attempt to get more detail about enantioselective behavior of fenoxaprop acid (FA) in the environment, using CDs as a remediation agent for FA and formulation additive for fenoxaprop-p-ethyl (FE). The significant difference between rac-FA and R-FA was not observed in their acute toxicity to S. obliquus and dissipation in S. obliquus suspension. RAMEB had no effect on either toxicity of FA to S. obliquus or dissipation of FA in S. obliquus suspension, and it also didn't change the extent of enantioselectivity in toxicity of FA to S. obliquus. But the addition of a certain amount of beta -CD and HP-beta -CD reduced the toxicity of FA to S. obliquus and increased dissipation of FA in S. obliquus suspension, as well as changed the enantioselectivity in toxicity of FA to S. obliquus. The results indicated beta-CD and HP-beta-CD could be used as a promising agent for remediation of aquatic contamination produced by FA, and RAMEB might be used as potential formulation additives for FE, the parent compound of FA, as RAMEB didn't decrease activity of R-FA and might be environmentally safer than the conventional additives.     

Effects of nano-copper(II) oxide and nanomagnesium oxide particles on activated sludge

Effects of nano-copper(II) oxide (nano-CuO) and nanomagnesium oxide (nano-MgO) particles on activated sludge endogenous respiration (aerobic digestion), biochemical oxygen demand (BOD) biodegradation, and nitrification were investigated through respiration rate measurement. For comparison, the effects of Cu(II) and Mg(II) ions on activated sludge were also studied. Results indicated that soluble Cu(II) has half maximum inhibitory concentration (IC50) values of 19, 5.5, 53, and 117 mg Cu/L for endogenous respiration, BOD biodegradation, ammonium oxidation, and nitrite oxidation, respectively. However, nano-CuO only inhibited BOD biodegradation at 240 mg Cu/L or more, and its associated toxicity was primarily caused by soluble Cu(II). In contrast, soluble Mg(II) was not toxic to activated sludge in the experimental concentration range, but nano-MgO inhibited BOD biodegradation and nitrification with IC50 values of 70 and 143 mg Mg/L, respectively. Further study indicated that the toxicity of nano-MgO resulted primarily from increased pH following MgO hydrolysis.     

Investigation of solution chemistry effects on sorption behavior of Cu(II) on ZSM-5 zeolite

The sorption of Cu(II) from an aqueous solution using ZSM-5 zeolite was investigated by batch technique under ambient conditions. Sorption was investigated as a function of pH, ionic strength, foreign ions, humic substances, and temperature. The results indicate that the sorption of Cu(II) on ZSM-5 zeolite is strongly dependent on pH. Sorption is dependent on ionic strength at low pH, but independent of ionic strength at high pH values. The presence of humic/fluvic acid (HA/FA) enhances the sorption of Cu(II) on ZSM-5 zeolite at low pH values, and reduces Cu(II) sorption at high pH values. Sorption isotherms were well simulated by the Langmuir model. Thermodynamic parameters (i.e., deltaH0, deltaS0 and deltaG0) for the sorption of Cu(II) were determined from temperature-dependent sorption isotherms at 293.15, 313.15, and 333.15 K, respectively. Results indicate that the sorption process of Cu(II) on ZSM-5 zeolite is spontaneous and endothermic.     

Influences of macroalga-derived dissolved organic carbon on the aquatic toxicity of copper and cadmium

In this study, the effect of dissolved organic carbon (DOC) derived from macroalga (Sargassum) on the acute toxicity of copper (Cu) and cadmium (Cd) to a freshwater cladoceran (Daphnia magna) was investigated. Potassium-loaded macroalga was incubated with ultrapure water to extract macroalgal DOC, which was then spiked with the constituents of the Elendt M7 hard water media. The 48 h median lethal concentration of Cu increased linearly with DOC levels but that of Cd was relatively independent of DOC levels (0-44 mg l(-1)). The independence of Cd toxicity on DOC level might be due to the competitive effect of high calcium concentrations in the media with Cd for the binding sites of DOC. The decreased Cu toxicity was a result of reduced Cu uptake as evidenced in a separate accumulation test. Also, the capability of the macroalgal DOC on reducing Cu toxicity was found to be comparable to DOC tested in other studies. Therefore, the present study suggested that the biosorption treatment process using macroalgae should consider the effect of DOC release from the biomass as a step of modifying the metal toxicity as well as influencing metal biosorption capacity.     

Toxic effect of metal cation binary mixtures to the seaweed Gracilaria domingensis (Gracilariales,Rhodophyta)

The macroalga Gracilaria domingensis is an important resource for the food, pharmaceutical, cosmetic, and biotechnology industries. G. domingensis is at a part of the food web foundation, providing nutrients and microelements to upper levels. As seaweed storage metals in the vacuoles, they are considered the main vectors to magnify these toxic elements. This work describes the evaluation of the toxicity of binary mixtures of available metal cations based on the growth rates of G. domingensis over a 48-h exposure. The interactive effects of each binary mixture were determined using a toxic unit (TU) concept that was the sum of the relative contribution of each toxicant and calculated using the ratio between the toxicant concentration and its endpoint. Mixtures of Cd(II)/Cu(II) and Zn(II)/Ca(II) demonstrated to be additive; Cu(II)/Zn(II), Cu(II)/Mg(II), Cu(II)/Ca(II), Zn(II)/Mg(II), and Ca(II)/Mg(II) mixtures were synergistic, and all interactions studied with Cd(II) were antagonistic. Hypotheses that explain the toxicity of binary mixtures at the molecular level are also suggested. These results represent the first effort to characterize the combined effect of available metal cations, based on the TU concept on seaweed in a total controlled medium. The results presented here are invaluable to the understanding of seaweed metal cation toxicity in the marine environment, the mechanism of toxicity action and how the tolerance of the organism.     

Growth performance and biochemical responses of three rice (Oryza sativa L.) cultivars grown in fly-ash amended soil

The disposal of fly-ash (FA) from coal-fired power stations causes significant economic and environmental problems. Use of such contaminated sites for crop production and use of contaminated water for irrigation not only decreases crop productivity but also poses health hazards to humans due to accumulation of toxic metals in edible grains. In the present investigation, three rice cultivars viz., Saryu-52, Sabha-5204, and Pant-4 were grown in garden soil (GS, control) and various amendments (10%, 25%, 50%, 75% and 100%) of FA for a period of 90 days and effect on growth and productivity of plant was evaluated vis-a-vis metal accumulation in the plants. The toxicity of FA at higher concentration (50%) was reflected by the reduction in photosynthetic pigments, protein and growth parameters viz., plant height, root biomass, number of tillers, grain and straw weight. However, at lower concentrations (10-25%), FA enhanced growth of the plants as evident by the increase of studied growth parameters. The cysteine and non-protein thiol (NP-SH) content showed increase in their levels up to 100% FA as compared to control, however, maximum content was found at 25% FA in Saryu-52 and Pant-4 and at 50% FA in Sabha-5204. Accumulation of Fe, Si, Cu, Zn, Mn, Ni, Cd and As was investigated in roots, leaves and seeds of the plants. Fe accumulation was maximum in all the parts of plant followed by Si and both showed more translocation to leaves while Mn, Zn, Cu, Ni and Cd showed lower accumulation and most of the metal was confined to roots in all the three cultivars. As was accumulated only in leaves and was not found to be in detectable levels in roots and seeds. The metal accumulation order in three rice cultivars was Fe > Si > Mn > Zn > Ni > Cu > Cd > As in all the plant parts. The results showed that rice varieties Saryu-52 and Sabha-5204 were more tolerant and could show improved growth and yield in lower FA application doses as compared to Pant-4. Thus, Sabha-5204 and Saryu-52 are found suitable for cultivation in FA amended agricultural soils for better crop yields.     

Sequential removal of heavy metals ions and organic pollutants using an algal-bacterial consortium

The residual algal-bacterial biomass from photosynthetically supported, organic pollutant biodegradation processes, in enclosed photobioreactors, was tested for its ability to accumulate Cu(II), Ni(II), Cd(II), and Zn(II). Salicylate was chosen as a model contaminant. The algal-bacterial biomass combined the high adsorption capacity of microalgae with the low cost of the residual biomass, which makes it an attractive biosorbent for environmental applications. Cu(II) was preferentially taken-up from the medium when the metals were present both separately and in combination. There was no observed competition for adsorption sites, which suggested that Cu(II), Ni(II), Cd(II), and Zn(II) bind to different sites and that active Ni(II), Cd(II) and Zn(II) binding groups were present at very low concentrations. Therefore, special focus was given to Cu(II) biosorption. Cu(II) biosorption by the algal-bacterial biomass was characterized by an initial fast cell surface adsorption followed by a slower metabolically driven uptake. pH, Cu(II), and algal-bacterial concentration significantly affected the biosorption capacity for Cu(II). Maximum Cu(II) adsorption capacities of 8.5+/-0.4 mg g-1 were achieved at an initial Cu(II) concentration of 20 mg l-1 and at pH 5 for the tested algal-bacterial biomass. These are consistent with values reported for other microbial sorbents under similar conditions. The desorption of Cu(II) from saturated biomass was feasible by elution with a 0.0125 M HCl solution. Simultaneous Cu(II) and salicylate removal in a continuous stirred tank photobioreactor was not feasible due to the high toxicity of Cu(II) towards the microbial culture. The introduction of an adsorption column, packed with the algal-bacterial biomass, prior to the photobioreactor reduced Cu(II) concentration, thereby allowing the subsequent salicylate biodegradation in the photobioreactor.     

Influence of toxicity and dissipation of racemic fenoxaprop and its R-enantiomer in Scenedesmus obliquus suspension by cyclodextrins

Cyclodextrins (CDs), a class of cyclic oligosaccharide molecules containing a variety of chiral centre, are capable of recognizing enantiomeric molecules through the formation of inclusion complexes. In this work, we selected three types of CDs, β-CD and its two derivatives, randomly methylated β-CD (RAMEB) and hydroxypropyl β-CD (HP-β-CD), to evaluate effects on toxicity of racemic fenoxaprop (rac-FA) and its R-enantiomer (R-FA) to freshwater alga Scenedesmus obliquus (S. obliquus) and their dissipation in S. obliquus suspension with and without CDs addition, respectively, in an attempt to get more detail about enantioselective behavior of fenoxaprop acid (FA) in the environment, using CDs as a remediation agent for FA and formulation additive for fenoxaprop-p-ethyl (FE). The significant difference between rac-FA and R-FA was not observed in their acute toxicity to S. obliquus and dissipation in S. obliquus suspension. RAMEB had no effect on either toxicity of FA to S. obliquus or dissipation of FA in S. obliquus suspension, and it also didn't change the extent of enantioselectivity in toxicity of FA to S. obliquus. But the addition of a certain amount of β -CD and HP-β -CD reduced the toxicity of FA to S. obliquus and increased dissipation of FA in S. obliquus suspension, as well as changed the enantioselectivity in toxicity of FA to S. obliquus. The results indicated β-CD and HP-β-CD could be used as a promising agent for remediation of aquatic contamination produced by FA, and RAMEB might be used as potential formulation additives for FE, the parent compound of FA, as RAMEB didn't decrease activity of R-FA and might be environmentally safer than the conventional additives.     

Monitoring behavioural responses to metals in gammarus pulex (L.) (Crustacea) with impedance conversion

An impedance conversion technique was used to study the behaviour of Gammarus pulex (L.) exposed to acutely toxic concentrations of Pb (0.01, 0.05, 0.1 and 0.5 mg Pb 1^-1) and to field concentrations of Cu (≤ 0.05 mg Cu 1^-1). Initial stress responses were studied during short-term exposure (1 h), and sublethal toxic effects were monitored during 7 (Pb) and 35 days (Cu), respectively. Exposure to Pb caused 30 % mortality and resulted in a bioconcentration factor (BCF) of 2700 at 0.5 mg Pb l^-1 after 168 h. Exposure to Cu polluted stream water caused no mortality within 35 days, and uptake was low (BCF 5.8). Gammarus pulex reacted with initial stress responses to metal exposure within 30 min (Cu) or 1 h (Pb). The reactions consisted of increased ventilation and decreased locomotion. Sublethal concentrations of Pb and Cu caused toxic effects on the behaviour of G. pulex after several days of exposure, consisting of increased ventilation and decreased locomotion. Impedance conversion is an appropriate method for detecting stress responses to metals and can be used in “early warning” biomonitoring systems as well as for acute and chronic behavioural toxicity testing.     

A comparison of acute toxicity of biodiesel, biodiesel blends, and diesel on aquatic organisms

The increased demand of alternative energy sources has created interest in biodiesel and biodiesel blends; biodiesel is promoted as a diesel substitute that is safer, produces less harmful combustion emissions, and biodegrades more easily. Like diesel spills, biodiesel can have deleterious effects on the aquatic environments. The effect of neat biodiesel, biodiesel blends, and diesel on Oncorhynchus mykiss and Daphnia magna was evaluated using acute toxicity testing. Static nonrenewal bioassays of freshwater organisms containing B100, B50, B20, B5, and conventional diesel fuel were used to compare the acute effects of biodiesel to diesel. Mortality was the significant end point measured in this study; percent mortality and lethal concentration (LC50) at different exposure times were determined from the acute toxicity tests performed. Trials were considered valid if the controls exhibited > 90% survival. Based on percentage of mortality and LC50 values, a toxicity ranking of fuels was developed.     

Effects of salinity,pH and temperature on the re-establishment of bioluminescence and copper or SDS toxicity in the marine dinoflagellate Pyrocystis lunula using bioluminescence as an endpoint

Pyrocystis lunula is a unicellular, marine, photoautotrophic, bioluminescent dinoflagellate. This organism is used in the Lumitox bioassay with inhibition of bioluminescence re-establishment as the endpoint. Experiments determined if acute changes in pH, salinity, or temperature had an effect on the organisms' ability to re-establish bioluminescence, or on the bioassay's potential to detect sodium dodecyl sulfate (SDS) and copper toxicity. The re-establishment of bioluminescence itself was not very sensitive to changes in pH within the pH 6-10 range, though reducing pH from 8 to levels below 6 decreased this capacity. Increasing the pH had little effect on Cu or SDS toxicity, but decreasing the pH below 7 virtually eliminated the toxicity of either compound in the bioassay. Lowering the salinity from 33 to 27 per thousandth or less resulted in a substantial decrease in re-establishment of bioluminescence, while increasing the salinity to 43 or 48 per thousandth resulted in a small decline. Salinity had little influence on the bioassay's quantification of Cu toxicity, while the data showed a weak negative relationship between SDS toxicity and salinity. Re-establishment of bioluminescence showed a direct dependence on temperature, but only at 10 degrees C did temperature have an obvious effect on the toxicity of Cu in this bioassay.     

Treatment and detoxification of a sanitary landfill leachate

The leachate from an old sanitary landfill (Gramacho Metropolitan Landfill, Rio de Janeiro) was characterized and submitted to coagulation and flocculation treatment followed by ozonation and ammonia stripping. The performance of the treatment was assessed by monitoring the removal of organic matter (COD and TOC), ammonium nitrogen and metals. Detoxification was assessed by determining acute toxicity, using the following organisms: Vibrio fisheri, Daphnia similis, Artemia salina and Brachydanio rerio. Membrane fractionation was employed to infer the range of molecular masses of the pollutants found in the effluent, as well as the toxicity associated to these fractions. Of the techniques under investigation, coagulation and flocculation followed by ammonia stripping were the most effective for toxicity and ammonium nitrogen removal. Membrane fractionation was effective for COD removal; however, acute toxicity was almost the same in all the fractionated samples. Ozonation was moderately effective for COD removal, but significant toxicity removal was only attained when high ozone doses were used.     

Patterns of metals and arsenic poisoning in Vibrio fischeri bacteria

The Microtox bioassay was used to establish dose-response curves for some toxic elements in aqueous solutions, namely, Zn(II), Pb(II), Cu(II), Hg(II), Ag(I), Co(II), Cd(II), Cr(VI), As(V) and As(III). Experiments were carried out at either pH 6.0 or pH 7.0 to indicate that pH may influence the measured toxicity of some elements due to pH-related changes of their chemical speciation. EC20 values, which represent a measurable threshold of toxicity, were determined for each element and were found to rank as Pb(II)>Ag(I)>Hg(II) approximately Cu(II)>Zn(II)>As(V)>Cd(II) approximately Co(II)>As(III)>Cr(VI). These values were compared to the limit concentrations allowed in industrial wastewater according to the official regulations in Catalonia (Spain). It appears that the Microtox test is sensitive enough for detecting some of the tested elements with respect to official regulations of Catalonia (Spain) dealing with pollution control, with the exception of cadmium, mercury, arsenate, arsenite and chromate.     

Effect of biochars on adsorption of Cu(II), Pb(II) and Cd(II) by three variable charge soils from southern China

The purpose of this study is to compare the relative contribution of different mechanisms to the enhanced adsorption of Cu(II), Pb(II) and Cd(II) by variable charge soils due to incorporation of biochars derived from crop straws. The biochars were prepared from the straws of canola and peanut using an oxygen-limited pyrolysis method at 350 °C. The effect of biochars on adsorption and desorption of Cu(II), Pb(II) and Cd(II) by and from three variable charge soils from southern China was investigated with batch experiments. Based on the desorption of pre-adsorbed heavy metals, the electrostatic and non-electrostatic adsorptions were separated. EDTA was used to replace the heavy metals complexed with biochars and to evaluate the complexing ability of the biochars with the metals. The incorporation of biochars increased the adsorption of Cu(II), Pb(II) and Cd(II) by the soil; peanut straw char induced a greater increase in the adsorption of the three metals. The increased percentage of Cd(II) adsorption induced by biochars was much greater than that for the adsorption of Cu(II) and Pb(II). Cu(II) adsorption on three variable charge soils was enhanced by the two biochars mainly through a non-electrostatic mechanism, while both electrostatic and non-electrostatic mechanisms contributed to the enhanced adsorption of Pb(II) and Cd(II) due to the biochars. Peanut straw char had a greater specific adsorption capacity than canola straw char and thus induced more non-electrostatic adsorption of Cu(II), Pb(II) and Cd(II) by the soils than did the canola straw char. The complexing ability of the biochars with Cu(II) and Pb(II) was much stronger than that with Cd(II) and thus induced more specific adsorption of Cu(II) and Pb(II) by the soils than that of Cd(II). Biochars increased heavy metal adsorption by the variable charge soils through electrostatic and non-electrostatic mechanisms, and the relative contribution of the two mechanisms varied with metals and biochars.     

Response of fluctuating asymmetry to arsenic toxicity: support for the developmental selection hypothesis

The effect of exposure to sodium arsenite during development was tested on adult fluctuating asymmetry (FA) in sternopleural bristle number, bristle number, body size and survivorship in Drosophila melanogaster. Three genetic strains of flies were used, CT-106, PVM and Oregon-R, and arsenite concentrations ranged from relatively mild, sub-lethal doses, to concentrations with pronounced negative effects on survivorship. At arsenite concentrations of 1.0 and 0.125 mM, mortality was on average 38% greater than in controls, and surviving flies emerged significantly smaller and had fewer bristles than controls. Neither the effect of arsenite or the genotype x environment interaction on asymmetry were significant. However, given the high mortality, any increase in FA could have been masked by the outcome of developmental selection against developmentally unstable phenotypes. We tested for this effect by contrasting FA values between (1) flies reared at the highest concentrations used previously, (2) flies reared at sub-lethal dosage, and (3) controls. Positional fluctuating asymmetry (PFA), which is expected to be a sensitive indicator of underlying developmental stability, was significantly reduced among flies reared at the highest concentration, and at which flies suffered significant mortality. Moreover, the slope of the regression relating mean PFA to emergence per bottle was significantly positive. These data support the hypothesis that developmental selection occurred in this experiment, and that the expected positive relationship between asymmetry and stress may be altered when the stressor eliminates individuals from the population. In contrast, FA of flies reared at sub-lethal dosage did not differ from that in controls, a result that fails to support the hypothesis that arsenite disrupts developmental stability. Our results call for caution in FA-based biomonitoring, especially of potentially lethal forms of stress, because in the presence of developmental selection, and under the common assumption that FA should increase under stress, erroneous conclusions may be drawn about the health and well being of a population. It is suggested that FA-based biomonitoring efforts integrate the use of FA with other bioindicators, and experimentally validate any expected FA-stress relationship before attempting to infer the presence of environmental stress.     

Characterization of heavy metal concentrations in the sediments of three freshwater rivers in Huludao City, Northeast China

Wuli River, Cishan River, and Lianshan River are three freshwater rivers flowing through Huludao City, in a region of northeast China strongly affected by industrialization. Contamination assessment has never been conducted in a comprehensive way. For the first time, the contamination of three rivers impacted by different sources in the same city was compared. This work investigated the distribution and sources of Hg, Pb, Cd, Zn and Cu in the surface sediments of Wuli River, Cishan River, and Lianshan River, and assessed heavy metal toxicity risk with the application of two different sets of Sediment Quality Guideline (SQG) indices (effect range low/effect range median values, ERL/ERM; and threshold effect level/probable effect level, TEL/PEL). Furthermore, this study used a toxic unit approach to compare and gauge the individual and combined metal contamination for Hg, Pb, Cd, Zn and Cu. Results showed that Hg contamination in the sediments of Wuli River originated from previous sediment contamination of the chlor-alkali producing industry, and Pb, Cd, Zn and Cu contamination was mainly derived from atmospheric deposition and unknown small pollution sources. Heavy metal contamination to Cishan River sediments was mainly derived from Huludao Zinc Plant, while atmospheric deposition, sewage wastewater and unknown small pollution were the primary sources for Lianshan River. The potential acute toxicity in sediment of Wuli River may be primarily due to Hg contamination. Hg is the major toxicity contributor, accounting for 53.3-93.2%, 7.9-54.9% to total toxicity in Wuli River and Lianshan River, respectively, followed by Cd. In Cishan River, Cd is the major sediment toxicity contributor, however, accounting for 63.2-66.9% of total toxicity.     

In situ immobilization of Cu(II) in soils using a new class of iron phosphate nanoparticles

This study tested the feasibility of using a new class of iron phosphate (vivianite) nanoparticles synthesized using sodium carboxymethyl cellulose (NaCMC) as a stabilizer for in situ immobilization of Cu(II) in soils. Transmission electron microscopy measurements demonstrated that the particle size was about 8.4+/-2.9 nm. Batch tests showed that nano-sized vivianite particles can effectively reduce the leachability and in vitro bioaccessibility of Cu(II) in three representative soils (calcareous, neutral, and acidic) at the low doses of 0.61 and 3.01 mg PO(4) g(-1) soil. The Cu leachability was evaluated by the toxicity characteristic leaching procedure and in vitro bioaccessibility was evaluated by the physiological based extraction test. In the case of soil amendment with nanoparticles in 3.01 mg PO(4) g(-1) soil, Cu leachability reduced 63-87% and Cu concentrations in TCLP extract decreased from 1.74-13.33 mg l(-1) to 0.23-2.55 mg l(-1) after those soils were amended for 56 d. Meanwhile, the bioaccessibility of Cu was reduced by 54-69%. Sequential extraction procedures showed the significant decrease of water soluble/exchangeable Cu(II) and carbonate bound fractions and concomitant increase of Cu residual fraction after the soils were amended with the nanoparticles, suggesting that the formation of copper phosphate minerals through precipitation and adsorption was probably responsible for the decrease of Cu availability in soils. Visual MINTEQ modeling further revealed that Cu(3)(PO(4))(2) and Cu(5)(PO(4))(3)OH were formed in the vivianite-solid Cu(II) system, resulting in the decreased solubility of the Cu(II) in the acidic pH range.     

Effects of copper and palladium on the reduction of bromate by Fe(0)

Bromate reduction by Fe(0) with incorporation of copper or palladium was investigated in batch tests. The incorporation of copper led to an increase in the rate of bromate reduction, while incorporation of palladium did not show any effect on bromate reduction by Fe(0), regardless of the bimetal application techniques (either simultaneous addition of Cu(II) or Pd(IV) into the Fe-BrO3- reaction system or using copper or palladium amended iron for bromate removal). Surface analyses by X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) techniques indicated that aqueous Cu(II) was reduced and incorporated into the iron surface to form Cu2O and Cu(0). Among these two species, pure Cu(0) is not an active electron donor to the bromate reduction reaction, as shown by there being no reduction from using Cu(0) powders alone and no enhancement by Fe(0) when physically mixed with Cu(0). Although it has been proposed in the literature that the enhancement of adsorption also contributes to the enhancement of chemical reduction, this is not the case here because adsorption decreased when Cu increased. The enhanced bromate reduction rate in the presence of copper observed here is most likely the result of the newly formed active Cu(I). The presence of PdO was evidenced by XPS but yielded no enhancement in bromate reduction. Finally, the Cu2O present on the iron surface because of copper impurities in commercially available iron was found to be involved in the bromate reduction and to accelerate the reduction rate.     

Characterization of primary precipitate composition formed during co-removal of Cr(VI) with Cu(II) in synthetic wastewater

BACKGROUND, AIMS AND SCOPE: Hexavalent chromium [Cr(VI)] cannot react with either carbonate or hydroxide to form chromium precipitates. However, by using a precipitation technology to treat plating wastewater containing Cr(VI), Cu(II), Ni(II) and Zn(II), approximately 78% of Cr(VI) (initial 60 mg/L) was co-removed with the precipitation of Cu(II), Ni(II) and Zn(II) (each 150 mg/L) by dosing with Na2CO3 (Sun 2003). Direct precipitation by forming Cu(II)-Cr(VI) precipitates followed by adsorption of Cr(VI) onto freshly formed Cu-precipitates was subsequently found to be the main mechanism(s) involved in Cr(VI) co-removal with Cu(II) precipitation by dosing Na2CO3 stepwise to various pH values (Sun et al. 2003). This study was. carried out to further characterize the formation of primary precipitates during the early stages of copper precipitation and simultaneous removal of Cr(VI) with Cu(II). METHODS: Test metal-solutions were prepared with industrial grade chemicals: CuCl2 x 2H2O, Na2SO4 and K2Cr2207. NaCO3 was added drop-wise to synthetic metal-solution to progressively increase pH. For each pH increment, removal of soluble metals was detected by atomic absorption spectrophotometer (AAS) and surface morphology of precipitates was analyzed by scanning electron microscope (SEM). To further characterize the formation of primary precipitates, a series of MINEQL+ thermodynamic calculations/analyses and equilibrium calculations/ analyses were conducted. RESULTS AND DISCUSSION: MINEQL+ thermodynamic calculation indicated that, for a system containing 150 mg/L Cu(II) and 60 mg/L Cr(VI) with gradual Na2CO3 dosing, if any precipitates can be formed at pH 5.0 or lower, it should be in the form of CuCrO4. Comparison tests using systems containing the same equivalent of Cu(II) plus Cr(VI) and Cu(II) plus SO4(2-) showed that the precipitation occurred at a pH of around 5.0 in the Cu(II)-Cr(VI) system and around 6.0 in the Cu(II)-SO4(2-) system. The discrepancy of the precipitation was indeed caused by the formation of Cu-Cr precipitates. The initiation of copper removal at pH around 5.0 for the Cu-Cr co-removal test was not attributable to the formation of Cu-CO3 precipitates, instead, it was most likely through the formation of insoluble Cu-Cr precipitates, such as CuCrO4 and CuCrO4 x 2Cu(OH)2. Experimental tests, equilibrium calculations, MINEQL+ thermodynamic calculations and surface morphologies for systems using higher concentrations of Cu(II) and Cr(VI) further verified the most probable composition of primary precipitates is copper-chromate. CONCLUSION: In the Cu-Cr co-removal test with Na2O3 dosing to increase pH and induce metal precipitation, copper-chromate precipitates are the primary precipitates produced and contribute to the initial simultaneous removal of copper and chromium.