Application of Adsorption and Ultrafiltration Processes for the Pre-treatment of Several Industrial Wastewater Streams

In this work ultrafiltration (UF) was coupled with suitable minerals and dried activated sludge for the pre-treatment of several industrial wastewater streams. The aim was to decrease heavy metal concentrations to low levels so that wastewater can be safely discharged into municipal sewers or biological wastewater treatment can take place without biomass inhibition problems. Industrial wastewater originating from metal plating, chemical and textile industries was employed. The experiments were conducted in a reactor where the UF membrane module was immersed. UF reduced the amount of heavy metals, but the performance was variable with removal efficiencies ranging from 20 to 99.7?%, depending on the metal type and on the wastewater initial characteristics. The prevailing wastewater characteristics were the pH, the presence of certain anions, the suspended solids concentration and the presence of competing cations. The addition of activated sludge and/or minerals could further increase heavy metal removal through the process of sorption. UF assisted by minerals could achieve variable colour and COD removal ranging from 22 to 94?% and 58 to > 99.9?% respectively. Minerals resulted in membrane fouling mitigation, while sludge adversely impacted on fouling.     

Removal of Pb(II), Cr(III) and Cr(VI) from Aqueous Solutions Using Alum-Derived Water Treatment Sludge

The sorption of Pb(II), Cr(III) and Cr(VI) from aqueous solution using alum-derived water treatment sludge was investigated using the batch adsorption technique. Samples of sludge from two separate water treatment plants were used (one where alum was used alone and one where it was used in combination with activated C). The sorption characteristics of the two samples were generally very similar. Sorption isotherm data for all three ions fitted equally well to both Freundlich and Langmuir equations. Maximum sorption capacity and indices of sorption intensity both followed the order: Cr(III)?>?Pb(II)?>?Cr(VI). Kinetic data correlated well with a pseudo-second-order kinetic model suggesting the process involved was chemisorption. Sorption was pH-dependant with percentage sorption of Cr(III) and Pb(II) increasing from <30% to 100% between pH?3 and 6 whilst that of Cr(VI) declined greatly between pH?5 and 8. HNO₃ at a concentration of 0.1?M was effective at removing sorbed Cr(III) and Pb(II) from the sludge surfaces and regeneration was successful for eight sorption/removal cycles. It was concluded that water treatment sludge is a suitable material from which to develop a low-cost adsorbent for removal of Cr and Pb from wastewater streams.     

Competition from Cu(II), Zn(II) and Cd(II) in Pb(II) Binding to Suwannee River Fulvic Acid

This is a study of trace metal competition in the complexation of Pb(II) by well-characterized humic substances, namely Suwannee River Fulvic Acid (SRFA) in model solutions. It was found that Cu(II) seems to compete with Pb(II) for strong binding sites of SRFA when present at the same concentration as Pb(II). However, Cd(II) and Zn(II) did not seem to compete with Pb(II) for strong binding sites of SRFA. These two metals did compete with Pb(II) for the weaker binding sites of SRFA. Heterogeneity of SRFA was found to play a crucial role in metal–SRFA interactions. The environmental significance of this research for freshwater is that even at relatively low Pb(II) loadings, the metals associated with lead in minerals, e.g. Cu(II), may successfully compete with Pb(II) for the same binding sites of the naturally occurring organic complexants, with the result that some of the Pb(II) may exist as free Pb²⁺ ions, which has been reported to be one of the toxic forms of Pb in aquatic environment.     

Batch Chromium(VI), Cadmium(II) and Lead(II) Removal from Aqueous Solutions by Horticultural Peat

The selectivity and uptake capacity of horticultural peat available in Romania was evaluated with respect to the removal of Cd(II), Cr(VI) and Pb(II) ions from aqueous solution. The kinetics, sorption capacities, selectivity and pH dependence of sorption were determined. The influence of metal concentration in solution is discussed in the terms of Langmuir and Freundlich isotherm and constants. Sorption capacities increased with increasing metal concentration in solution. For solutions containing 300 mg/l of metal, the observed uptake capacities were 20 mg Cd(II)/g peat, 15 mg Cr(VI)/g peat and 30 mg Pb(II)/g peat. The study proved that horticultural peat is a suitable material for the removal of the studied heavy metal ions from aqueous solutions, achieving removal efficiencies higher than 90%, and could be considered as a potential material for treating effluent polluted with Cd(II), Cr(VI) and Pb(II) ions.     

Separation and preconcentration of Cd(II), Cu(II), Ni(II), and Pb(II) in water and food samples using Amberlite XAD-2 functionalized with 3-(2-nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione and determination by inductively coupled plasma-atomic emission spectrometry

A separation and preconcentration procedure was developed for the determination of trace amounts of Cd(II), Cu(II), Ni(II), and Pb(II) in water and food samples using Amberlite XAD-2 fuctionalized with a new chelating ligand, 3-(2-nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione (Amberlite XAD-2-NPTT). The chelating resin was characterized by Fourier transform infrared spectroscopy (FT-IR) and used as a solid sorbent for enrichment of analytes from samples. The sorbed elements were subsequently eluted with 10 mL of 1.0 M HNO(3), and the eluates were analyzed by inductively coupled plasma-atomic emission spectrometry. The influences of the analytical parameters including pH, amount of adsorbent, eluent type and volume, flow rate of the sample solution, volume of the sample solution, and effect of matrix on the preconcentration of metal ions have been studied. The optimum pH for the sorption of four metal ions was about 6.0. The limits of detection were found to be 0.22, 0.18, 0.20, and 0.16 μg L(-1) for Cd(II), Cu(II), Ni(II), and Pb(II), respectively, with a preconcentration factor 60. The proposed method was applied successfully for the determination of metal ions in water and food samples.     

Effect of carboxylic and thiol ligands (oxalate, cysteine) on the kinetics of desorption of Hg(II) from kaolinite

Sorption and desorption of Hg(II) on clay minerals can impact the biogeochemical cycle and bio-uptake of Hg in the environment. We studied the kinetics of the desorption of Hg(II) from kaolinite as affected by oxalate and cysteine, representing the ligands with carboxylic and thiol groups of different affinities for Hg(II). The effects of pH (3, 5, and 7), ligand concentration (0.25 and 1.0?mM), and temperature (15??C, 25??C, and 35??C) on the Hg(II) desorption were investigated through desorption kinetics. Our study showed that the Hg(II) desorption was pH dependent. In the absence of any organic ligand, >90% of the previously adsorbed Hg(II) desorbed at pH?3 within 2?h, compared to <10% at pH?7. Similar results were observed in the presence of oxalate, showing that it hardly affected the Hg(II) desorption. Cysteine inhibited the Hg(II) desorption significantly at all the pH tested, especially in the first 80?min with the desorption less than 20%, but the inhibition of the desorption appeared to be less prominent afterwards. The effect of the ligand concentration on the Hg(II) desorption was small, especially in the presence of oxalate. The effect of temperature on the Hg(II) desorption was nearly insignificant. The effect of the organic acids on the Hg(II) sorption and desorption is explained by the formation of the ternary surface complexes involving the mineral, ligand, and Hg(II). The competition for Hg(II) between the cysteine molecules adsorbed on the particle surfaces and in the solution phase probably can also affect the Hg(II) desorption.     

A comparative study of Cd,Cr(III), Cr(VI), Hg,and Pb uptake by minerals and soil materials

The pH dependency of Cd, Cr(III), Cr(VI), Hg, and Pb uptake by 14 different types of minerals and soil materials has been studied. The solids were interacted with metal solutions separately in a batch procedure, and the percentage of metal uptake of different metal-solid combinations was compared and evaluated. The results were quantified by the pH values at which 10, 50 and 90% of the metal uptake took place. Physical and chemical characteristics of the solids were correlated with metal uptake. The results verify the importance of geochemical parameters of soils such as organic content, type of clay mineral, presence of complexing ions, and redox-potential for controlling metal uptake. Retention of Cd, Cr(VI), Hg, and Pb was found to be strongly dependent on organic content of the materials studied. Montmorillonite (in bentonite and smectite) showed the highest uptake of Cd, Cr(III) and Pb among all minerals and soil materials, while illite and kaolinite showed lower uptake than the soils. At low pH, the uptake percentage of Cr(VI) by organic soils was higher than that of any of the other metal ions. The uptake of Hg was low in comparison to other cations, which may be explained by formation of soluble Hg(CI)₂° or Hg(CI)⁴ _2? complexes.     

Chemically Modified Silica Gel with N-(2-aminoethyl)-Salicylaldimine for Simultaneous Solid Phase Extraction and Preconcentration of Cu(II), Ni(II), Cd(II) and Zn(II) in waters

In this study, N-(2-aminoethyl)salicylaldimine bonded silica gel was synthesized and characterized using Fourier transform infrared and C, H, N elemental analysis. The analytical conditions such as the pH and volume of the solution, flow rates of the sample solution and the type of eluent to achieve the simultaneous preconcentration of Cu(II), Ni(II), Cd(II) and Zn(II) were optimised using the modified silica gel loaded column using a solid phase extraction technique. Samples (50?C500?ml) containing metal ions at optimal pH of 8 were passed through the column filled with the modified silica gel at 7?ml min^?1 and then elution was achieved using 5?ml of 0.25?M HCl. The concentrations of metal ions in the eluates were determined using flame atomic absorption spectrometry (FAAS). The effects of matrix ions were also studied and none of the major ions interfered to the proposed method. The accuracy of the developed method was validated using a certified reference water sample (Ontario Lake water, NWTMDA-54.4). The method was successfully applied to the analysis of various natural water samples. The adsorption capacities of the modified silica gel for Cu(II), Ni(II), Cd(II) and Zn(II) ions were determined and found to be 0.332, 0.261, 0.130 and 0.375?mmol g^?1, respectively.     

Simultaneous determination of Cd(II), Cu(II), Pb(II), and Zn(II) in citrus essential oils by derivative potentiometric stripping analysis

Citrus essential oils are widely used in the food, cosmetics, and pharmaceutical industries, so the determination of heavy metals content is of great importance to guarantee their quality. The present work deals with the quantification of Cd(II), Cu(II), Pb(II), and Zn(II) in different varieties of citrus essential oils, using derivative potentiometric stripping analysis. Two different metals extraction procedures, involving concentrated hydrochloric acid treatment and acid-alcoholic dissolution, are tested on lemon, mandarin, sweet orange, and bergamot essential oils, and they give very similar results. Cd(II), Cu(II), Pb(II), and Zn(II) recovery tests spanned from 95 to 100.50%, providing evidence that metals quantification remained unaffected by the cleanup steps of the two procedures. The repeatability of the hydrochloric acid extraction method, applied on different varieties of essential oils, is >95.00% for Cd(II), Cu(II), Pb(II), and Zn(II), whereas the repeatability of the acid-alcoholic dissolution method is >93.00% for Cu and Cd only in lemon oil. Detection limits obtained for the four analytes, using both procedures, ranged from 0.10 to 0.98 ng g(-)(1) in lemon, mandarin, sweet orange, and bergamot essential oils.     

Influence of different mineral and Organic pesticide treatments on Cd(II), Cu(II), Pb(II), and Zn(II) contents determined by derivative potentiometric stripping analysis in Italian white and red wines

This paper deals with the use of derivative potentiometric stripping analysis (dPSA) as a rapid and precise method to determine Cd(II), Cu(II), Pb(II), and Zn(II) levels in red and white wine samples from Sicily, Campania, and Tuscany and to investigate the possible connection between the content of these metals and the pesticide treatments used in vine-growing to control plant diseases and pests. dPSA allowed direct quantitation of heavy metals in acidified wines without any sample pretreatment. Mean recoveries of Cd(II), Cu(II), Pb(II), and Zn(II) ranged from 95.5 to 99.2% for white wine samples and from 96.1 to 100.0% for red wine samples. The obtained results showed that Cd(II) was not found in any sample and that Cu(II), Pb(II), and Zn(II) levels were always lower than the toxicity limits in both fungicide- and water-treated wines. Nevertheless, the contents of metals were increased in samples from organic and inorganic pesticides treatment with respect to the water-treated samples. In particular, quinoxyfen, dinocap-penconazole, and dinocap applications considerably increased Cu(II) and Zn(II) contents in white and red wines. The levels of lead were significantly raised by azoxystrobin and sulfur treatments.     

A Study of Diffusive Gradients in Thin Films for the Chemical Speciation of Zn(II), Cd(II), Pb(II), and Cu(II): The Role of Kinetics

The lability and mobility of Zn(II)–, Cd(II)–, Pb(II)–, and Cu(II)–humic acid complexes were studied using diffusive gradients in thin films (DGT). A unique feature of this research was (1) the use of DGTs with diffusive layer thicknesses ranging from 0.4 to 2.0 mm to study lability and mobility of Zn(II)–, Cd(II)–, Pb(II)–, and Cu(II)–humic acid complexes, combined with (2) the application of a competing ligand exchange (CLE) method using Chelex 100, the same chelating resin that is used in DGT, to study the kinetic speciation. The CLE experiments were run immediately after the completion of the DGT experiments, thereby allowing effects of the competing ligand to be separated from the effects introduced by the use of the polyacrylamide gel that is used in DGT. The results indicate that Zn(II) and Cd(II) tend to form more labile and more mobile complexes with humic acid than Pb(II) or Cu(II). The dissociation rate constants of Zn(II), Cd(II), and Pb(II) were found to increase with the ionic potential of the metal, suggesting that the binding between some trace metals and humic acid has a significant covalent component. Furthermore, the results suggest that the Eigen mechanism may not be strictly obeyed for metals such as Cu(II) which have high rate constants of water exchange, k _w. Consequently, the markedly slow kinetics of Cu(II)-HA species suggests that the usual equilibrium assumption may not be valid in freshwaters.     

Sorption Behavior of Arsenate by Mg-Bearing Minerals at Hyperalkaline Condition: Implications for Oxyanions Sequestration During the Use and Disposal of Alkaline Wastes

The utilization and disposal of alkaline waste materials such as slag and coal fly ash as cement aggregates and raw materials in cement manufacturing can pose environmental and health hazards because these waste materials usually contain elevated concentration of toxic elements. This study examined the possibility of controlling the pore water chemistry of these waste materials in order to induce the secondary mineral formation of Mg-bearing minerals as major sorbing solids for oxyanions during the utilization and disposal of alkaline wastes. The formation of Mg-bearing minerals was examined at ambient temperature and alkaline pH conditions in the Mg?CSi?CAl system. The interaction of Mg-bearing minerals with oxyanions using arsenate as an analog was examined during and after mineral formation. The results revealed that the generated Mg-bearing mineral phases were smectite and brucite in Mg?CSi system and hydrotalcite and serpentine in Mg?CSi?CAl system. Moreover, hydrotalcite, serpentine, brucite, and smectite phases formed under low Si ratio showed high sorption capacity for arsenate, but only high Al content hydrotalcite and serpentine showed substantial irreversible fraction of sorbed arsenate. Hence, the generation of these kinds of hydrotalcite and serpentine phases as scavengers for oxyanions must be considered during the utilization and disposal of alkaline wastes.     

Removal of Mercury Ions from Mixed Aqueous Metal Solutions by Natural and Modified Zeolitic Minerals

Research works on the removal of mercury from water by zeolitic mineralshow that small quantities of this element are sorbed. In this work the mercury sorption from aqueous solutions in the presence and absence of Cu(II), Ni(II) and Zn(II) onto a Mexican zeolitic mineral unmodified and modified with cysteamine hydrochloride or cystamine dihydrochloride was investigated in acidic pH. The zeolitic minerals were characterized by thermogravimetric analysis, scanning electron microscopy, X-ray diffraction and FTIR. The sorption kinetics behavior and the retention isotherms for mercury were determined in the natural and treated zeolitic mineral samples. It was found that the amounts of sulfur on the modified zeolitic minerals were 0.375 (cysteamine hydrochloride) and 0.475 (cystamine dihydrochloride) mmol g^-1, which were not saturated to their total capacities of adsorption for the maximum concentration used (0.310 mM). Under the experimental conditions, the retention of mercury was the highest for the zeolitic minerals treated with the organic compounds, with adsorption capacities ranging from 0.0107 to 0.0509 mmol Hg g^-1.The retention was not affected by the presence of others heavy metals studied in this work as expected.     

Interactive Sorption of Metal Ions and Humic Acids onto Mineral Particles

The sorption of metal ions (Pb2+, Zn2+ and Cu2+) and soil humic acids (HA) from aqueous solutions onto mineral particles (sand, calcite and clay) was investigated using a batch equilibrium system. The sorption reactions in two- component systems (heavy metals-mineral particles and humic acids- mineral particles), as well as interactions in three-component system (heavy metals-humic acids-mineral particles) were examined. Results showed that the presence of humic acids, dissolved or bound onto mineral surfaces, considerably influenced the fixation of heavy metals. The various effects, depending on mineral type, humic concentration and specific metal-ion, were observed in three- component system. Sorption of Cu2+-ions on all minerals studied rapidly increased as the concentration of dissolved HA increased. The amount of Pb2+-ions sorbed on sand slightly decreased, while on kaolin increased between 15 and 20%. Sorption of Zn2+-ions on all minerals studied decreased at pH 4. At pH 5.5 the sorption of Zn2+-ions onto calcite decreased, while on kaolin and sand increased as a function of the humic acid concentration giving the curve with maximum at c(HA) = 2.5 mmol C L-1. At pH 6.5 sorption onto kaolin and sand increased. This effect occurs as a result of the conditional stability constant of Zn-HA complexes increasing at higher pH which in turn promotes the chelation of Zn2+-ions to mineral- bound humic substances. The enhanced sorption of metal ions from the aqueous phase in three-component systems is not only the result of mineral sorption of free metals but also the result of chelation with HA sorbed on the mineral surface.     

Heavy metal sorption on soil minerals affected by the siderophore desferrioxamine B: the role of Fe(III) (hydr)oxides and dissolved Fe(III)

Phytoextraction of heavy metals from polluted soils has often been found to be limited by the bioavailability of the pollutants. Inorganic or organic ligands are occasionally used as complexing agents to enhance the mobility of the heavy metals. However, the opposite effect is also possible. We studied the influence of the hydroxamate siderophore desferrioxamine B (DFOB) on the sorption of Cu, Zn and Cd to clay minerals, with the emphasis on the role of dissolved Fe(III) and Fe(III) minerals. Depending on the surface charge of the minerals and on pH, sorption of heavy metals can be either enhanced or diminished. We show here that this effect of DFOB disappears if dissolved Fe(III) is added to suspensions of clay minerals in excess to DFOB. We found that the solid Fe(III) phases ferrihydrite and goethite did not impede the effect of DFOB on the sorption of heavy metal, however. Between pH 4 and 10, DFOB completely prevented Cu sorption on ferrihydrite. A strong mobilizing effect was also observed for Zn, but not for Cd. In presence of goethite, concentrations of dissolved Cu, Zn and Cd were enhanced only above approximately pH 5, 7 and 8, respectively. Below these pH values the binding of these metals to goethite was even stronger with than without DFOB. In the absence of heavy metals, DFOB‐promoted dissolution of ferrihydrite was much faster than that of goethite due to the larger surface area of ferrihydrite. In the alkaline pH range, where sorption of DFOB on the surfaces of the iron oxides was greater, dissolution of both minerals was reduced.     

Comparative Assessment of Al(III) and Cd(II) Biosorption onto Turbinaria conoides in Single and Binary Systems

The present work investigated the ability of inactive brown seaweed, Turbinaria conoides, to biosorb aluminum(III) and cadmium(II) ions in both single and binary systems. Initial experiments were undertaken to determine the influence of pH and biosorption isotherms of each metallic ion. Owing to the presence of carboxylic groups, T. conoides exhibited high uptake capacity towards Al(III) and Cd(II) through ion-exchange mechanism. In the case of Al(III), T. conoides exhibited maximum biosorption at pH 4 with a capacity of 2.37?mmol/g, whereas the highest Cd(II) biosorption occurred at pH 5 with a capacity of 0.96?mmol/g. For both metal ions, T. conoides exhibited fast kinetics. Several models were used to describe isotherm (Langmuir, Freundlich, Redlich-Peterson, and Toth) and kinetic (pseudo-first and pseudo-second order) data. Desorption and reuse of T. conoides biomass in three repeated cycles was successful with 0.1?M HCl as elutant. In binary systems, the presence of Cd(II) severely affected Al(III) uptake by T. conoides. Compared to single-solute systems, Al(III) uptake was reduced to 56% compared to only 27% for Cd(II). Based on the model parameters regressed from the respective monometal systems, multicomponent Langmuir and Freundlich models were used to predict binary (Al + Cd) system of which the multicomponent Freundlich model was able to describe with good accuracy.     

A Comparison of Water Treatment Sludge and Red Mud as Adsorbents of As and Se in Aqueous Solution and Their Capacity for Desorption and Regeneration

The adsorption of As(III), As(V), Se(IV) and Se(VI) by seawater neutralized red mud and alum water treatment sludge was investigated and compared using the batch adsorption technique. For water treatment sludge, adsorption of As(V), Se(IV) and Se(VI), at equimolar concentrations of added metalloid, declined with increasing pH. The decline was rapid above pH?4.0 for Se(VI), above pH?5.0 for Se(IV) and above pH?6.0 for As(V). Adsorption of As(III) increased with increasing pH up to pH?9.0 and then declined. For red mud, adsorption of As(V), Se(IV) and Se(VI) showed a maximum at about pH?5.0 and for As(III) adsorption remained relatively constant over the pH range 2.0?C10.0 after which it declined. Water treatment sludge removed 50?% or more of solution As(V) between pH?2.0 and 10.8, Se(IV) between 2.0 and 8.9, Se(VI) between 2.0 and 5.8 and As(III) between 8.4 and 10.9. By contrast, red mud showed less than 25?% adsorption of added Se(VI) and As(III) over the entire pH range tested (2.0?C12.0) and reached 50?% or more for As(V) only over the pH range 4.0?C6.9 and for Se(IV) between pH?4.3 and 5.6. At pH?5.0, adsorption of As(III) and Se(IV) was better described by the Langmuir than Freundlich equation but the reverse was the case for As(V) and Se(VI). Kinetic data for adsorption of all four oxyanions onto both adsorbents correlated well with a pseudo-second-order kinetic model suggesting the process involved was chemisorption. NaOH was more effective at removing adsorbed metals from both adsorbents than HNO₃. Water treatment sludge maintained its As(III) and Se(IV) adsorption capability at greater than 70?% of that added over eight successive cycles of adsorption/regeneration using 0.5?M NaOH as a regenerating agent. By contrast, for red mud, As(V) adsorption capacity declined very rapidly after three adsorption/desorption cycles and that for Se(IV) it decreased progressively with increasing numbers of cycles. It was concluded that water treatment sludge is a suitable material to develop as a low-cost adsorbent for removal of heavy metal oxyanions from wastewater streams.     

Competitive Removal of Heavy Metals from Aqueous Solutions by Montmorillonitic and Calcareous Clays

A batch sorption method was used to study the removal of few toxic metals onto the Late Cretaceous clays of Aleg formation (Coniacian–Lower Campanian system), Tunisia, in single, binary and multi-component systems. The collected clay samples were used as adsorbents for the removal of Pb(II), Cd(II), Cu(II) and Zn(II) from aqueous solutions. Results show that the natural clay samples were mainly composed of silica, alumina, iron and magnesium oxides. N₂-adsorption measurements indicated mesoporous materials with modest specific surface area of <71 m²/g. Carbonate minerals were the most influencing parameters for heavy metal removal by natural clays in both single and multi-element systems. The affinity sequence was Pb(II)>Cu(II)>Zn(II)>Cd(II) due to the variable physical properties of the studied metals. The maximum adsorption capacity reached 131.58 mg/g in single systems, but decreased to <50.10 mg/g in mixed systems. In single, binary and muti-element systems, the studied clay samples removed substantial amounts of heavy metals, showing better effectiveness than the relevant previous studies. These results suggest that the studied clay samples of the Late Cretaceous clays from Tunisia can be effectively used as natural adsorbents for the removal of toxic heavy metals in aqueous systems.     

Effect of Copper(II), Lead(II), and Zinc(II) on Growth and Sporulation of Halophytophthora from Taiwan Mangroves

This study evaluated the effect of lead (Pb(II)), zinc (Zn(II)) and copper (Cu(II)) on growth and sporulation of four Halophytophthora species (Halophytophthora vesicula, Halophytophthora elongata, Halophytophthora spinosa var. lobata, and an oogonia-producing Halophytophthora sp.) isolated from different mangrove sites in Taiwan. Results show that all isolates grew well or even better at 1 ppm concentration of the heavy metals tested. Growth of all test isolates was totally inhibited at 500 ppm, except for H. spinosa var. lobata exposed to Zn(II). For sporulation, all isolates produced moderate to abundant zoosporangia or oogonia at 1 ppm Pb(II) and Zn(II). Production of zoosporangia by H. vesicula, H. elongata and H. spinosa var. lobata was significantly affected or totally inhibited at 1 ppm Pb(II) and Zn(II) and all concentrations of Cu(II). Abnormal oogonia were produced by Halophytophthora sp. at 10 ppm Cu(II) and 100 ppm of the three heavy metals. In general, Cu(II) and Zn(II) were found to be the most toxic, and the least toxic was Pb(II). H. spinosa var. lobata was the most tolerant to all the heavy metals, while H. vesicula and H. elongata were the most sensitive. Results of this study shows that increased concentrations of Pb(II), Cu(II), and Zn(II) in the mangrove environment can significantly affect growth and impair normal reproduction of Halophytophthora species.     

有机磷与土壤矿物相互作用及其环境效应研究进展

土壤有机磷是土壤环境中重要的磷组分,其在环境中的界面反应影响着磷素的迁移、转化、生物有效性以及环境行为。本文主要总结了土壤中典型有机磷在矿物表面的吸附-解吸、溶解-沉淀等反应特性和微观机制,以及有机磷-矿物相互作用对有机磷形态、金属离子界面反应行为,以及矿物胶体化学稳定性与溶解转化的影响等环境效应。土壤有机磷可含多个磷酸基团,相对分子质量大,电荷密度高,通过界面反应与环境矿物发生强烈的相互作用,并影响矿物的电荷性质、共存金属离子的吸附特性、以及胶体化学稳定性。有机磷界面反应特性和机制受矿物类型和结晶度、有机磷相对分子质量、pH、温度和共存离子等因素的影响。有机磷在矿物表面的吸附密度一般随着体系pH、矿物结晶度和有机磷相对分子质量的升高而降低。有机磷一般可在矿物表面形成内圈络合物,某些情况下还存在氢键作用,甚至转化形成表面沉淀。有机磷和金属离子在矿物表面的吸附一般存在协同效应(尤其是在低pH条件下),即金属离子促进了有机磷的吸附,有机磷也促进金属离子的固定;吸附机制因反应体系而异,主要包括形成三元表面络合物和表面沉淀等,多数时候存在多种机制的共同作用。最后讨论了环境中有机磷与矿物相互作用的主要研究热点和方向。