Cadmium adsorption on vermiculite, zeolite and pumice: batch experimental studies

Batch experiments were performed to evaluate the combined effects of ionic activity, pH, and contact time on the cadmium sorption in three different minerals, vermiculite, zeolite, and pumice, commonly employed as substrata in nurseries and recently considered for their potential use in remediation methods. The extent of cadmium sorption was vermiculite>zeolite>pumice, as shown by the Langmuir and Freundlich parameters, and it was highly dependent on mineral characteristics. The percentage of cadmium sorption in zeolite and vermiculite did not depend on cadmium concentration, while in pumice this percentage was positively correlated to the initial cadmium concentration. At low cadmium concentrations (30-120 microM), the metal sorbed on zeolite was mainly present in the nonexchangeable form (70%) at levels much higher than those found for vermiculite and pumice. The primary variable responsible for determination of cadmium mobility in these minerals was confirmed to be pH. The ionic concentrations of Hoagland nutrient solution were significantly modified by both pH and mineral composition, while the presence of cadmium caused no changes. With vermiculite and zeolite, the time-course of cadmium sorption was related to mineral composition to a greater extent than to cadmium concentration. While with pumice, the percentage of cadmium sorbed after 6 weeks was lower than with the other two minerals, and it was inversely correlated to the initial cadmium concentration.     

Cation-pi bonding: a new perspective on the sorption of polycyclic aromatic hydrocarbons to mineral surfaces

Recent molecular modeling and spectroscopic studies have suggested that relatively strong interactions can occur between aromatic pi donors and metal cations in aqueous solutions. The objective of this study was to characterize potential cation-pi interactions between pi donors and exchangeable cations accumulated at mineral surfaces via both spectroscopic and batch sorption methods. Quadrupolar splitting in deuterium nuclear magnetic resonance ((2)H NMR) spectroscopy for d(2)-dichloromethane, d(6)-benzene, and d(8)-toluene (C(6)D(5)- moiety) in aqueous suspensions of a Na-saturated reference montmorillonite unambiguously indicated the ordering of solute molecules with respect to the clay surface. The half line broadening (Delta nu(1/2)) of (2)H NMR of d(6)-benzene in montmorillonite suspensions showed that soft exchangeable cations generally resulted in more benzene sorption compared with harder cations (e.g., Ag(+) > Cs(+) > Na(+) > Mg(2+), Ba(2+)). In batch sorption experiments, saturating minerals (e.g., porous silica gels, kaolinite, vermiculite, montmorillonite) with a soft transition metal or softer base cations generally increased the polycyclic aromatic hydrocarbon (PAH) sorption relative to harder cations (e.g., Ag(+) > Cs(+) > K(+) > Na(+); Ba(2+) > Mg(2+)). Sorption of phenanthrene to Ag(+)-saturated montmorillonite was much stronger compared with 1,2,4,5-tetrachlorobenzene, a coplanar non-pi donor having slightly higher hydrophobicity. In addition, a strong positive correlation was found between the cation-dependent sorption and surface charge density of the minerals (e.g., vermiculite, montmorillonite > silica gels, kaolinite). These results, coupled with the observations in (2)H NMR experiments with montmorillonite, strongly suggest that cation-pi bonding forms between PAHs and exchangeable cations at mineral surfaces and affects PAH sorption to hydrated mineral surfaces.     

Evaluation of soils for use as liner materials: a soil chemistry approach

Movement of NH(4)(+) below animal waste lagoons is generally a function of the whole-lagoon seepage rate, soil mineralogy, cations in the lagoon liquor, and selectivity for NH(4)(+) on the soil-exchange sites. Binary exchange reactions (Ca(2+)-K(+), Ca(2+)-NH(4)(+), and K(+)-NH(4)(+)) were conducted on two soils from the Great Plains and with combinations of these soils with bentonite or zeolite added. Binary exchanges were used to predict ternary exchanges Ca(2+)-K(+)-NH(4)(+) following the Rothmund-Kornfeld approach and Gaines-Thomas convention. Potassium and NH(4)(+) were preferred over Ca(2+), and K(+) was preferred over NH(4)(+) in all soils and soils with amendments. Generally, the addition of bentonite did not change cation selectivity over the native soils, whereas the addition of zeolite did. The Rothmund-Kornfeld approach worked well for predicting equivalent fractions of cations on the exchanger phase when only ternary-solution phase compositions were known. Actual swine- and cattle-lagoon solution compositions and the Rothmund-Kornfeld approach were used to project that native soils are predicted to retain 53 and 23%, respectively, of the downward-moving NH(4)(+) on their exchange sites. Additions of bentonite or zeolite to soils under swine lagoons may only slightly improve the equivalent fraction of NH(4)(+) on the exchange sites. Although additions of bentonite or zeolite may not help increase the NH(4)(+) selectivity of a liner material, increases in the overall cation exchange capacity (CEC) of a soil will ultimately decrease the amount of soil needed to adsorb downward-moving NH(4)(+).     

Influence of quaternary ammonium on sorption of selected metal cations onto clinoptilolite zeolite

Clay minerals and zeolites have large cation exchange capacities, which enable them to be modified by cationic surfactant to enhance their sorption of organic and anionic contaminants. In this study, the influence of quaternary ammonium surfactants on sorption of five metal cations (Cs+, Sr+, La3+, Pb2+, and Zn2+) onto a clinoptilolite zeolite was investigated. Generally, the metal cation sorption capacity and affinity for the zeolite decreased, indicating that presorbed cationic surfactants blocked sorption sites for metal cations, as the surfactant loading on the zeolite increased. Cesium and Pb2+ sorption was affected to a small extent, indicating that selective sorption for Cs+ and specific sorption for Pb2+ play an important role in addition to cation exchange. Sorption of cationic surfactants on zeolite preloaded with different metal cations showed a strong correlation with the chain length of the surfactant tail group, while the roles of the charges and types of the metal cations were minimal. As the chain length increases, the critical micelle concentration decreases and the surfactant molecules become more hydrophobic, resulting in progressive bilayer coverage. Desorption of presorbed metal cations by cationic surfactants was strongly affected by the surfactant chain length and metal type. More metal cations, particularly Sr2+ and Zn2+, desorbed with an increase in surfactant chain length. The results, in combination with those from organic and oxyanion sorption on surfactant-modified zeolite, may be used for future surfactant modification to target sorption and desorption of a specific type of contaminant or a mixture of different types of contaminants.     

Sorption of cadmium and zinc from aqueous solutions by zeolite 4A, zeolite 13X and bentonite

The sorption and desorption of cadmium and zinc on zeolite 4A, zeolite 13X and bentonite has been studied using batch sorption studies. Parameters such as equilibrium time, effect of pH and sorbent dose were studied. The sorbents exhibited good sorption potential for cadmium and zinc with a peak value at pH 6.0 and 6.5, respectively. The sorption followed the Freundlich sorption model. More than 70% sorption occurred within 20 min and equilibrium was attained at around 90 min for the three sorbents. The metals sorption by zeolite 4A was higher than that by zeolite 13X and bentonite. The desorption studies were carried out using NaCl solution and the effect of NaCl concentration on desorption was also studied. Maximum desorption of 76% for cadmium and 80% for zinc occurred with 10% NaCl.     

Efficiency of removal of cadmium from aqueous solutions by plant leaves and the effects of interaction of combinations of leaves on their removal efficiency

Removal of cadmium from aqueous solutions using 20 species of plant leaves and combinations of these leaves have been studied. Several factors affecting the removal efficiency have been studied. The most efficient types of plant leaves for the removal of cadmium are those of styrax, plum, pomegranate and walnut. The interaction effect of the combined leaf samples on the efficiency of removal of cadmium has been found to be additive in combinations involving styrax plant leaves but seems to be antagonistic in all other combinations. The optimum experimental conditions for removal of cadmium have been found to be at pH 4.1, using high concentrations of naturally dried plant leaves, using ground leaves and to remove cadmium from agitated aqueous solutions. The percentage of metal removed at an initial cadmium concentration of 10mg/l by the most efficient types of leaves have been found to be 85% for styrax leaves, 85% for plum leaves, 80% for pomegranate leaves, 78% for walnut leaves and 77% for meddler leaves. The presence of foreign ions or complexing agents has been found to reduce the efficiency of removal of cadmium by plant leaves. About 80-85% of the cadmium in charged plant leaves has been released under the influence of changing the pH of the solution, addition of competing ions and the addition of EDTA. The results of removal of cadmium by plant leaves have been found to follow the Freundlich adsorption isotherm, first-order reaction with respect to cadmium and to have intra-pore diffusion as the rate-limiting step.     

Alkaline hydrothermal conversion of fly ash precipitates into zeolites 3: the removal of mercury and lead ions from wastewater

In this paper, the utilisation of zeolites synthesised from fly ash (FA) and related co-disposal filtrates as low-cost adsorbent material were investigated. When raw FA and co-disposal filtrates were subjected to alkaline hydrothermal zeolite synthesis, the zeolites faujasite, sodalite and zeolite A were formed. The synthesised zeolites were explored to establish its ability to remove lead and mercury ions from aqueous solution in batch experiments, to which various dosages of the synthesised zeolites were added. The test results indicated that when increasing synthesised zeolite dosages of 5-20 g/L were added to the acid mine drainage (AMD) wastewater, the concentrations of lead and mercury in the wastewater were reduced accordingly. The lead concentrations were reduced from 3.23 to 0.38 and 0.17 microg/kg, respectively, at an average pH of 4.5, after the addition of raw FA zeolite and co-disposal filtrate zeolite to the AMD wastewater. On the other hand, the mercury concentration was reduced from 0.47 to 0.17 microg/kg at pH=4.5 when increasing amounts of co-disposal filtrate zeolite were added to the wastewater. The experimental results had shown that the zeolites synthesised from the co-disposal filtrates were effective in reducing the lead and mercury concentrations in the AMD wastewater by 95% and 30%, respectively.     

An unconventional method for the recovery of caustic soda from spent Al-rich pickling solutions

This work presents an unconventional procedure for the recovery of spent Al-rich caustic soda solutions from the pickling of dies for the production of aluminium extrusions. Caustic soda was regenerated at roughly 70%, by precipitating aluminate, after addition of a silica source, in the form of zeolite A, a microporous material that is widely used in many technological sectors. It was shown that the process is reliable and can be repeated for several cycles, provided the concentration of the caustic soda solution is suitably restored. The by-product obtained, zeolite A, proved to be a high-grade material with performance as a cation exchanger and physical sorbent that is certainly comparable to that reported in literature (e.g., cation exchange capacity equal to 5.14 meq g(-1) vs. 5.48 meq g(-1) and water vapour adsorption capacity of 26.5% vs. 27.6% at 16 torr and 298 K). The economics of the process, although not examined yet, would appear generally favourable, considering that zeolite A is a valuable by-product which widely covers the costs for the recovery of the spent solutions. There are, therefore, significant prospects for the use of zeolite A, particularly as a builder in detergent formulation.     

Metal immobilization in soils using synthetic zeolites

In situ immobilization of heavy metals in contaminated soils is a technique to improve soil quality. Synthetic zeolites are potentially useful additives to bind heavy metals. This study selected the most effective zeolite in cadmium and zinc binding out of six synthetic zeolites (mordenite-type, faujasite-type, zeolite X, zeolite P, and two zeolites A) and one natural zeolite (clinoptilolite). Zeolite A appeared to have the highest binding capacity between pH 5 and 6.5 and was stable above pH 5.5. The second objective of this study was to investigate the effects of zeolite addition on the dissolved organic matter (DOM) concentration. Since zeolites increase soil pH and bind Ca, their application might lead to dispersion of organic matter. In a batch experiment, the DOM concentration increased by a factor of 5 when the pH increased from 6 to 8 as a result of zeolite A addition. A strong increase in DOM was also found in the leachate of soil columns, particularly in the beginning of the experiment. This resulted in higher metal leaching caused by metal-DOM complexes. In contrast, the free ionic concentration of Cd and Zn strongly decreased after the addition of zeolites, which might explain the reduction in metal uptake observed in plant growth experiments. Pretreatment of zeolites with acid (to prevent a pH increase) or Ca (to coagulate organic matter) suppressed the dispersion of organic matter, but also decreased the metal binding capacity of the zeolites due to competition of protons or Ca.     

Life cycle inventory of recycling portable nickel–cadmium batteries

In this study, the environmental impact of recycling portable nickel–cadmium (NiCd) batteries in Sweden is evaluated. A life cycle assessment approach was used to identify life cycle activities with significant impact, the influence of different recycling rates and different time boundaries for emissions of landfilled metals. Excluding the user phase of the battery, 65% of the primary energy is used in the manufacture of batteries while 32% is used in the production of raw materials. Metal emissions from batteries to water originate (96–98%) from landfilling and incineration. The transportation distance for the collection of batteries has no significant influence on energy use and emissions. Batteries manufactured with recycled nickel and cadmium instead of virgin metals have 16% lower primary energy use. Recycled cadmium and nickel metal require 46 and 75% less primary energy, respectively, compared with extraction and refining of virgin metal. Considering an infinite time perspective, the potential metal emissions are 300–400 times greater than during the initial 100 years. From an environmental perspective, the optimum recycling rate for NiCd batteries tends to be close to 100%. It may be difficult to introduce effective incitements to increase the battery collection rate. Cadmium should be used in products that are likely to be collected at the end of their life, otherwise collection and subsequent safe storage in concentrated form seems to offer the best solution to avoid dissipative losses.     

Interparticle diffusion and thermodynamic modeling studies for the removal of heavy metals using mixed adsorbents in industrial effluents

Pollution of water, air, and soil by industrial effluents is a major problem nowadays. A variety of contaminants are too responsible for changing the physicochemical properties of the receiving body. There are practical treatment solutions available to clean up contaminants from various resources. The term “adsorption” refers to one of them. The purpose of the research work is to remove heavy metals from industrial effluent. Mixed adsorbents prepared from activated charcoal and bone charcoals were used to remove the copper and cadmium ions. The experiment carried out in a batch operation and modeling of these data for intraparticle diffusion and thermodynamic calculations were reported in this research work. At optimum operating condition pH 6; metal ion concentration 50 mg/L; dose 5 g/L; agitation 180 rpm and temperature 40°C maximum 99.41% copper ions and 88.12% cadmium ion removal was achieved. Cadmium ions were well fitted in the thermodynamic model compared to copper ions, as demonstrated by the higher correlation coefficient R² (0.9824) value. Intra particle diffusion demonstrated that film diffusion was a rate-limiting step at the start of the reaction, while microporous intraparticle diffusion was the rate-determining phase later on. A Fourier transformation infrared spectroscopy, X-ray diffraction, and scanning electron micrography analysis confirmed the suitability of mixed adsorbents for the removal of cadmium and copper metal ions.     

Removal and recycling of copper from aqueous solutions using treated Indian barks

Removal of copper from aqueous solutions containing 100–1000 ppm, using different Indian bark species, was performed on laboratory scale. The percentage removal of metal ions depends on the solution pH, bark species and time. The efficiency of copper removal by the used raw barks increases with a rise of solution pH and reaches a maximum of about 65–78% around pH 4–5. However, the decontaminated aqueous solutions were colored due to the dissolution of soluble organic compounds contained in the raw bark. This increases the biological and chemical oxygen demand (BOD and COD) of the solutions as well as the total organic carbon content (TOC). For this reason, raw bark should be treated either by chemical or biological means. Such treatment will allow the extraction of the soluble organic compounds and increase the chelating capacity and efficiency of the treated bark. Depending on the pH value, the chelating efficiency of treated barks is about 1.2–2.2 times that of the raw ones. Moreover, the retention capacity of the Indian treated bark varies from about 42–51 mg/g of dry bark. It is equal to or higher than that of common European species. About 1.8 mols of H₃O⁺ are released, by the treated barks, for every mol of chelated copper ions. Moreover, scanning electron microscopy (SEM) observations show uniform distribution of metal ions throughout the copper saturated bark. Infra red (IR) spectra suggest that the copper ions are chelated to hydroxyl and/or carboxyl functional groups of organic compounds contained in the treated bark. It seems that the interaction of the copper ions with the bark follows a cation exchange mechanism. This hypothesis is supported by elution experiments that allow recovery of about 99% of the contained copper. The retention capacity of the treated bark is almost constant after five cycles of chelation–elution, suggesting that the ‘life time cycle' is sufficiently long for continuous industrial application. The spent copper loaded barks can either be incinerated or pyrolysed. It generates solids containing either ≈80% of CuO or ≈14% of Cu°, respectively. Such materials can be used either in the secondary or primary copper production, thus offering a friendly environmental solution of effluents' treatment. The suggested process can be used as an alternative to the classical technologies for effluent decontamination. It is also efficient for polishing effluents treated by other methods.     

Implications of cation exchange on clay release and colloid-facilitated transport in porous media

Column experiments were conducted to study chemical factors that influence the release of clay (kaolinite and quartz minerals) from saturated Ottawa sand of different sizes (710,360, and 240 microm). A relatively minor enhancement of clay release occurred when the pH was increased (5.8 to 10) or the ionic strength (IS) was decreased to deionized (DI) water. In contrast, clay release was dramatically enhanced when monovalent Na+ was exchanged for multivalent cations (e.g., Ca2+ and Mg2+) on the clay and sand and then the solution IS was reduced to DI water. This solution chemistry sequence decreased the adhesive force acting on the clay as a result of an increase in the magnitude of the clay and sand zeta potential with cation exchange, and expansion of the double layer thickness with a decrease in IS to DI water. The amount of clay release was directly dependent on the Na+ concentration of the exchanging solution and on the initial clay content of the sand (0.026-0.054% of the total mass). These results clearly demonstrated the importance of the order and magnitude of the solution chemistry sequence on clay release. Column results and scanning electron microscope (SEM) images also indicated that the clay was reversibly retained on the sand, despite predictions of irreversible interaction in the primary minimum. One plausible explanation is that adsorbed cations increased the separation distance between the clay-solid interfaces as a result of repulsive hydration forces. A cleaning procedure was subsequently developed to remove clay via cation exchange and IS reduction; SEM images demonstrated the effectiveness of this approach. The transport of Cu2+ was then shown to be dramatically enhanced by an order of magnitude in peak concentration by adsorption on clays that were released following cation exchange and IS reduction.     

Prediction of metal-adsorption behaviour in the remediation of water contamination using indigenous microorganisms

In recent years, the adsorption of heavy metal cations onto bacterial surfaces has been studied extensively. This paper reports the findings of a study conducted on the heavy metal ions found in mine effluents from a mining plant where Co²⁺ and Ni²⁺ bearing minerals are processed. Heavy metal ions are reported to be occasionally present in these mine effluents, and the proposed microbial sorption technique offers an acceptable solution for the removal of these heavy metals. The sorption affinity of microorganisms for metal ions can be used to select a suitable microbial sorbent for any particular bioremediation process. Interactions of heavy metal ions (Co²⁺ and Ni²⁺) and light metal ions (Mg²⁺ and Ca²⁺) with indigenous microbial cells (Brevundimonas spp., Bacillaceae bacteria and Pseudomonas aeruginosa) were investigated using the Langmuir adsorption isotherm, pseudo second-order reaction kinetics model and a binary-metal system. Equilibrium constants and adsorption capacities derived from these models allowed delineation of the effect of binding affinity and metal concentration ratios on the overall adsorption behaviour of microbial sorbents, as well as prediction of performance in bioremediation systems. Although microbial sorbents used in this study preferentially bind to heavy metal ions, it was observed that higher concentrations (>90 mg/?) of light metal ions in multi-metal solutions inhibit the adsorption of heavy metal ions to the bacterial cell wall. However, the microbial sorbents reduced Ni²⁺ levels in the mine-water used (93–100% Ni²⁺ removal) to below the maximum acceptable limit of 350 μg/?, established by the South African Bureau of Standards. Competition among metal ions for binding sites on the biomaterial surface can occur during the bioremediation process, but microbial sorption affinity for heavy metal ions can enhance their remediation in dilute (<5 mg/? heavy metal) wastewaters.     

Lead removal from contaminated water using mineral adsorbents

This study records experiments undertaken to determine the suitable conditions for the use of naturally occurring minerals (talc, chalcopyrite and barite) as an adsorbent for the removal of lead ions from liquid wastes. The adsorption of lead ions from solutions containing different initial lead concentrations (50, 100, 200, 400, 600, 800 and 1000 mg l^–1 Pb as lead nitrate) using different size fractions (<63 m, 63–150 m) of talc, chalcopyrite and barite at different pH (3, 5, 7 and 9) and different adsorption times (24, 48, 72 and 96 hr) was examined. The results revealed that of the studied minerals, the chalcopyrite fraction at 63–150 m showed the highest adsorption capacity. The adsorption data of Pb ions was also analyzed with the help of the Langmuir and Freundlich models to evaluate the mechanistic parameters associated with the adsorption process. The adsorption isotherms obtained from the Langmuir and Freundlich equations were generally linear and the adsorption of Pb by the studied minerals was correlated with the adsorption maximum and binding energy constant of the Langmuir equation and equilibrium partition constant and binding partition coefficient of the Freundlich equation. It was concluded that the equilibrium time of adsorption was 72 hr at an optimum pH from 7 to 9. This technique might be successfully used for the removal of lead ions from liquid industrial wastes and wastewater.     

Rhizosphere acidification and cadmium uptake by strawberry clover

Strawberry clover (Trifolium fragiferum L.) is a hardy legume found in indigenous or introduced populations throughout the world. Tolerance to saline and alkaline soils, flooding, and heavy metals make it a good prospect for reclamation projects. The research, described here, was conducted to: (i) characterize the morphological variation in plants from available seed sources, (ii) evaluate cadmium uptake and tolerances over a wide range of morphological variants, and (iii) elucidate the variability in the effects of roots on rhizosphere pH and the relationship to cadmium uptake. Seeds from selected accessions were planted in the greenhouse for comparison of morphological variation. The accessions examined had a mean height of 10.7+/-7 cm. Accessions 254916 and 237925 are tall with high rhizosphere pH values and might be useful in phytoremediation. Strawberry clover accessions were also grown hydroponically to examine differences in cadmium uptake. The ability of strawberry clover roots to change rhizosphere pH and take up cadmium was examined using culture tubes containing nutrient agar, a moderate level of cadmium, and a pH indicator dye. The results provided evidence for a negative correlation between rhizosphere pH and cadmium uptake.     

Rhizospheric mobilization and plant uptake of radiocesium from weathered micas: I. Influence of potassium depletion

Potassium depletion in the soil solution around plant roots promotes the root uptake of radiocesium. However, it can also induce the transformation of mica through the release of interlayer K. In bulk soil, the formation of frayed edge sites (FES) with a high selectivity for Cs adsorption is usually related with mica weathering. We studied the effect of K level in the nutrient solution on the root-induced weathering of phlogopite as well as on the root uptake of radiocesium by willow (Salix viminalis L. var. Orm). The willows were grown for 7 wk in column lysimeters filled with a quartz-phlogopite mixed substrate continuously irrigated with nutrient solutions differing in K concentration (0-2 mM). From a potassium supply of 0.4 mM downward, we observed a decrease in root uptake of potassium as well as an increase in (i) potassium release from phlogopite, (ii) degree of transformation of phlogopite into vermiculite, and (iii) root uptake of radiocesium. Increasing K depletion had thus two effects: a decrease of the root uptake of potassium and an increase of phlogopite weathering in the rhizosphere, both of which promoted the root uptake of radiocesium.     

Plant uptake of cadmium-109 and zinc-65 at different temperature and organic matter levels

The uptake of 109Cd and 65Zn and their stable isotopes by ryegrass (Lolium multiflorum Lam.), grown on two different soil types, was investigated in climatically controlled growth chambers at 9 and 21 degrees C. The soils were treated with 0 and 4% organic matter (pig [Sus scrofa] manure) and spiked with 109Cd and 65Zn before sowing. The organic matter addition resulted in increased uptake of the 109Cd, Cd, and Zn by ryegrass, but the uptake of 65Zn was decreased. The latter effect was ascribed to isotopic dilution of 65Zn as the amount of stable Zn in the plant tissues increased with the organic matter addition. The effect of temperature was more pronounced than that of organic matter addition, and the uptake of both 109Cd and 65Zn and their stable isotopes was higher in ryegrass grown at 21 degrees C than that grown at 9 degrees C. Results from fractionation and speciation analysis of soil cadmium and zinc were correlated with plant uptake, and there was a good consistency between observed plant uptake and the physico-chemical forms of cadmium and zinc in soil and soil solution presumed to be plant available.     

Adsorption of isoxaflutole degradates to aluminum and iron hydrous oxides

Isoxaflutole is a preemergence herbicide that has been marketed as a substitute for atrazine. It is rapidly transformed to a more stable and soluble diketonitrile degradate (DKN) after field application and can further degrade to a benzoic acid degradate (BA) within soil. However, no previous research has been conducted to investigate DKN and BA sorption to metal oxide minerals. The primary objective of this research was to elucidate the interactions of DKN and BA with synthetic hydrous aluminum and iron oxides (HAO and HFO, respectively) to understand how variably charged minerals may influence adsorption of these compounds in soil. The herbicide degradates did adsorb to HAO and HFO, and the data were well described by the Freundlich model (R2 > 0.91), with Nvalues ranging from 0.89 to 1.2. Adsorption isotherms and Kd values demonstrate that BA is adsorbed to HFO to a greater extent than other degradate-mineral combinations that were studied. The degree of hysteresis between adsorption/desorption isotherms was characterized as slight (hysteresis index values < 1.7), suggesting weak DKN and BA retention to HFO and HAO oxide surfaces. Degradate adsorption was observed to greatly diminish as suspension pH increased. Attenuated total reflectance-Fourier transform infrared spectra show no evidence that DKN or BA adsorb to mineral surfaces as inner-sphere complexes under hydrated conditions. Instead DKN and BA adsorb to positively charged metal oxide surfaces as outer-sphere or diffuse ion swarm complexes via electrostatic attraction. This research indicates that metal oxides may serve as important retardants for DKN and BA migration through acidic soils enriched with aluminum and iron oxides.     

Cadmium in aquatic microcosms: Implications for screening the ecological effects of toxic substances

A two-phase set of experiments was conducted to address some of the problems inherent in ecological screening of toxic substances in aquatic microcosms. Phase I was a 4×4 factorial experiment dealing with the interactive effects of cadmium and nutrients in static microcosms. Phase II was a 2×4 factorial experiment using flowthrough microcosms to study temporal aspects of system behavior in response to nutrient loading and chronic versus acute cadmium perturbations. Nutrient enrichment resulted in increased biomass and metabolic activity in both static and flowthrough microcosms. Cadmium treatments generally resulted in a decrease in abundance of grazing crustaceans and a subsequent increase in community respiration, suggesting a change in community structure from a grazing to a detritus food chain. Of the variables measured, community metabolism, community composition, and output/input ratios of nitrate-nitrogen were the most useful indicators of system response to cadmium. Nutrient enrichment significantly influenced cadmium effects with respect to most of the variables measured; high levels of enrichment reduced the effects of cadmium. For screening the ecological effects of toxic chemicals, a series of experiments is proposed, including 1) relatively simple static microcosms, 2) flow through microcosms, and 3) more detailed but selective studies in microcosms derived from specific ecosystems. Each step yields increasingly more information and serves as a guide for subsequent experiments; in addition, each step more closely approximates natural ecosystems.