Predicting the rate and extent of cadmium and copper desorption from soils in the presence of bacterial extracellular polymer

The movement of cationic transition metals through the subsurface is strongly retarded by sorption to the porous media. However, dissolved organic ligands can compete with soil surfaces by providing binding sites for metals in solution. An extracellular polymer produced by a bacterium isolated from soil was used in this study to observe and model the influence of a naturally occurring ligand on the release of adsorbed metals from two test soils. Experimental results show that the presence of dissolved extracellular polymer enhanced the rate and extent of desorptive release of soil-bound cadmium and copper. A kinetic model that uses a gamma distribution of rate constants to account for the physical and chemical heterogeneity of the soil matrix was employed to describe the release of cadmium and copper in batch experiments. Model parameters describing soil, metal and extracellular polymer interactions were obtained through separate experiments. With these parameters the model successfully predicted the influence of dissolved polymer on the rate and extent of release of cadmium and copper from soil in independent batch experiments. These results suggest that the presence of natural metal-binding ligands such as bacterial extracellular polymers can act to increase the driving force for desorption by lowering the aqueous concentration of free unbound metals in solution.     

Removal of zinc, copper and lead by natural zeolite-a comparison of adsorption isotherms

An uptake of zinc (Zn), copper (Cu), and lead (Pb) from aqueous solutions by ion exchange on natural zeolitic tuff has been studied. The Croatian zeolite clinoptilolite from the Donje Jesenje deposit has been used as a natural ion exchanger. The efficiency of removal is higher for Pb and Cu than for Zn ions. Measured concentrations of Si in the liquid phase identify the detachment of the aluminosilicate structure during ion exchange in the presence of H(+) and OH(-) ions. The adsorption isotherm equations; Langmuir-Freundlich, Redlich-Petersen, Toth, Dubinin-Radushkevich, modified Dubinin-Radushkevich, and Lineweawer-Burk were derived from the basic empirical equations, and used for calculation of ion exchange parameters. The best fitting of experimental results to the proposed isotherms was observed in models that assume that ionic species bind first at energetically most favorable sites, with multi-layer adsorption taking place subsequently.     

Removal of lead ions from industrial waste water by different types of natural materials

The adsorption capacity of some natural materials for lead such as animal bone powder, active carbon, Nile rose plant powder, commercial carbon and ceramics was studied. The V/m ratio has been chosen to be 500 ml/g. The adsorption process was affected by various parameters such as contact time, pH and concentration of lead solution. The lead uptake percent reaches equilibrium state after 15, 30, 45 and 120 min for bone powder, active carbon, plant powder and commercial carbon, respectively. The uptake percent of lead increased by increasing pH value. The sequence of lead uptake percent (% adsorption) at constant pH from certain concentration of lead nitrate solution by the different natural materials is in the order: bone powder > active carbon > plant powder > commercial carbon. The uptake percent of lead is increased by decreasing the concentration of lead at constant pH. The capacity of lead adsorbed from nitrate solution by the different natural materials increased by increasing pH value. The synthetic and industrial waste-water samples were treated by using the different natural materials (contact time 3h, pH = 4). The percent removal of lead was 100% by bone powder, 90% by active carbon, 80% by plant powder and 50% by commercial carbon. There was no removal of lead by ceramics. This may be due to the presence of high percent of lead in the constituent of ceramics (372 mg/g).     

Mechanism of lead adsorption from aqueous solutions using an adsorbent synthesized from natural condensed tannin

Adsorption is a method for removing lead from wastewater. The adsorption of lead on a new adsorbent synthesized from natural condensed tannin has been investigated using a series of batch adsorption experiments. The study on the adsorption mechanism indicates that the adsorbent performed in aqueous solutions as an ionic exchanger whose end group was sodium ion (Na(+)). One lead (II) ion (Pb(2+)) was adsorbed onto the adsorbent by taking the place of two Na(+) ions. The maximum exchangeable Na(+) present on the adsorbent was measured with the proton titration experiments and it was up to 1.0 mmol x Na(+)g(-1) dry adsorbent. To a significant extent, pH influenced the extraction of lead from aqueous solutions. The lead removal efficiency was up to 71%, 87% and 91% with initial solution pH at 3.0, 3.6 and 4.2, respectively. The Langmuir equation fitted the adsorption isotherm data well. The maximum adsorption capacity of lead calculated was 57.5, 76.9 and 114.9 mg lead g(-1) dry adsorbent at initial solution pH of 3.0, 3.6 and 4.2, respectively. Therefore, the adsorbent does offer favorable characteristics in lead removal from acidic wastewater.     

Removal of copper ions from aqueous solutions by a steel-making by-product

A study is made of the use of a steel-making by-product (rolling mill scale) as a material for removing Cu(2+) ions from aqueous solutions. The influence of contact time, initial copper ion concentration and temperature on removal capability is considered. The removal of Cu(2+) ions from an aqueous solution involves two processes: on the one hand, the adsorption of Cu(2+) ions on the surface of mill scale due to the iron oxides present in the latter; and on the other hand, the cementation of Cu(2+) onto metallic iron contained in the mill scale. Rolling mill scale is seen to be an effective material for the removal of copper ions from aqueous solutions.     

Impact of galvanic corrosion on lead release from aged lead service lines

Partial lead service line replacement (PLSLR) may be performed when tap water lead concentrations exceed the action level and in association with water main replacement or other maintenance. Partially replacing lead pipes with copper tubing can create a galvanic couple if the lead and copper are connected by a metal coupling, which can potentially enhance lead release by galvanic corrosion. The effect of two types of couplings, brass and plastic, on lead release after a simulated PLSLR was investigated in a set of laboratory-scale experiments. Experiments were conducted in a recirculation flow mode with intermittent stagnation periods using aged lead pipes harvested from Providence, RI. Release of both dissolved and particulate lead was higher for the brass-coupled systems than for the plastic-coupled systems, and galvanic corrosion was the primary cause of significant particulate lead release from the brass-coupled systems. For brass-coupled systems, longer stagnation times resulted in dramatically more release of particulate lead. Sampling of different volumes following stagnation showed that lead release for the brass-coupled systems was locally much higher in the region closest to the coupling. The impact of galvanic corrosion persisted for the six weeks of the experiment.     

Selection of an adsorbent for lead removal from drinking water by a point-of-use treatment device

The removal of lead from drinking water was investigated to develop a point-of-use water filter that could meet the regulation imposed by the new European Directive 98-83 lowering lead concentration in drinking water below 10 μg L⁻¹. The objective of this research was to assess the potential of different adsorbents (zeolites, resins, activated carbon, manganese oxides, cellulose powder) to remove lead from tap water with a very short contact time. To begin, the repartition of the lead species in a tap water and a mineral water was computed with the computer model CHESS. It showed that in bicarbonated waters lead is mainly under lead carbonate form, either in the aqueous or in the mineral phase. Batch experiments were then conducted to measure the equilibrium adsorption isotherms of the adsorbents. Then, for five of them, dynamic experiments in micro-columns were carried out to assess the outlet lead concentration level. Three adsorbents gave rise to a leakage concentration lower than 10 μg L⁻¹ and were then selected for prototypes experiments: chabasite, an activated carbon coated with a synthetic zeolite and a natural manganese oxide. The proposed method clearly showed that the measurement of equilibrium isotherms is not sufficient to predict the effectiveness of an adsorbent, and must be coupled with dynamic experiments.     

Characterization of copper bioreduction and biosorption by a highly copper resistant bacterium isolated from copper-contaminated vineyard soil

Copper is an essential but toxic heavy metal that negatively impacts living systems at high concentration. This study presents factors affecting copper bioremoval (bioreduction and biosorption) by a highly copper resistant monoculture of Pseudomonas sp. NA and copper bioremoval from soil. Seven bacteria resistant to high concentration of Cu(II) were isolated from enrichment cultures of vineyard soils and mining wastes. Culture parameters influencing copper bioreduction and biosorption by one monoculture isolate were studied. The isolate was identified by 16S rRNA gene sequence analysis as a Pseudomonas sp. NA (98% similarity to Pseudomonas putida, Pseudomonas plecoglossicida and other Pseudomonas sp.). The optimal temperature for growth was 30 °C and bioremoval of Cu(II) was maximal at 35 °C. Considerable growth of the isolate was observed between pH 5.0 and 8.0 with the highest growth and biosorption recorded at pH 6.0. Maximal bioreduction was observed at pH 5.0. Cu(II) bioremoval was directly proportional to Cu(II) concentration in media. Pseudomonas sp. NA removed more than 110 mg L^− 1 Cu(II) in water within 24 h through bioreduction and biosorption at initial concentration of 300 mg L^− 1. In cultures amended with 100 mg L^− 1, 20.7 mg L^− 1 of Cu(II) was biologically reduced and more than 23 mg L^− 1 of Cu(II) was biologically removed in 12 h. The isolate strongly promoted copper bioleaching in soil. Results indicate that Pseudomonas sp. NA has good potential as an agent for removing copper from water and soil.     

Performance predictions of mature experimental constructed wetlands which treat urban water receiving high loads of lead and copper

The treatment efficiencies of vertical-flow wetland filters containing macrophytes and granular media of different adsorption capacities were investigated. Different concentrations of lead and copper sulphate were added to urban stream inflow water in order to simulate pre-treated (pH adjustment assumed) mine wastewater. After 1 year of operation, the metal mass load rate was increased by a factor of approximately 4.6. No breakthrough of metals was recorded. The use of macrophytes and adsorption media did not enhance heavy metal reduction significantly after 13 months of operation. A correlation analysis indicated strong positive correlations between conductivity on one side and other variables including temperature, total solids, dissolved oxygen and the redox potential on the other side. Some expensive or time-consuming variables (e.g., biochemical oxygen demand) can be predicted with less expensive ones (e.g., dissolved oxygen and temperature). The associated absolute mean errors were <10%.     

Assessment of Al-Madra clay as an adsorbent of copper ions from aqueous solutions

Al-Madra clay, a local, cheap and readily available material in Qatar, was tested for the removal of copper ions from aqueous solutions. Batch experiments of copper ion adsorption onto natural and treated clay in different conditions were undertaken. Different types of activated Al-Madra clay were used, such as Na-clay, Al-clay, thermal-clay and cyclohexane-clay. Thermally treated clay achieved the highest removal of Cu ions, followed by Al-clay, cyclohexane-clay, and finally Na-clay. A maximum of 50% adsorption of copper ions can be achieved using the natural clay while about 72% adsorption can be achieved when the clay is thermally treated. The amount of copper adsorbed by untreated Al-Madra clay was dependent on the process conditions; increasing with an increase in pH and initial metal concentration but decreasing with an increase in sorbent concentration. The increase in temperature from 5 to 50°C resulted in only a very slight increase in copper uptake by untreated Al-Madra clay.      

Effects of blending of desalinated water with treated surface drinking water on copper and lead release

This study examined effects of desalinated water on the corrosion of and metal release from copper and lead-containing materials. A jar test protocol was employed to examine metal release from copper and lead-tin coupons exposed to water chemistries with varying blending ratios of desalinated water, alkalinities, pHs and orthophosphate levels. Increasing fractions of desalinated water in the blends resulted in non-monotonic changes of copper and lead release, with generally lower metal concentrations in the presence of desalinated water, especially when its contribution increased from 80% to 100%. SEM examination showed that the increased fractions of desalinated water were associated with pronounced changes of the morphology of the corrosion scales, likely due to the influence of natural organic matter. This hypothesis was corroborated by the existence of correlations between changes of the ζ-potential of representative minerals (malachite and hydrocerussite) and metal release. For practical applications, maintaining pH at 7.8 and adding 1 mg/L orthophosphate as PO₄ were concluded to be adequate to decrease copper and lead release. Lower alkalinity of desalinated water was beneficial for blends containing 50% or more desalinated water.     

Sorption of copper by olive mill residues

A study on olive mill residues (OMR) as copper adsorbing material is reported in this work. A rough characterization of this waste material has been performed, by microanalysis and SEM pictures. Sorption tests with suspended OMR evidenced copper removal from solution, of about 60% in the investigated experimental conditions. The COD release in solution was also monitored during biosorption. Considering that it was significant, OMR washings with water were performed before biosorption. In this case the COD release in solution was reduced to less than 600 mg/L after two washings, while the OMR metal sorption properties did not change. Regenerated residues by acid solutions gave a copper removal of about 40%, in the same experimental conditions of the first adsorption test: regeneration with EDTA at different concentrations suggested that it presents a damage of adsorption active sites. On the other hand, the use of HCl and CaCl₂ led to completely regenerate the biosorbent material. Tests were also performed with a column filled with 80 g of OMR and the breakpoint was demonstrated to take place after that about 1 L solution was treated in the investigated experimental conditions. Regeneration tests permitted to demonstrate that a concentration factor of about 2 can be obtained in no-optimized conditions, highlighting the possibility of using OMR for the treatment of metal bearing effluents. The main advantage of the process would be the ‘‘low cost’’ biosorbing material, considering that it represents a waste in the olive oil production.     

Adsorption mechanism-based screening of cyclodextrin polymers for adsorption and separation of pesticides from water

A rational screening of cyclodextrin-based polymer (CDP), in terms of the relationship between adsorption potential and adsorbent-adsorbate, was investigated to adsorb and separate pesticides from water. Seven spherical porous CDPs were prepared with onefold or composite cyclodextrin(s) as complex and epichlorohydrin as cross-linking reagent. The adsorption kinetics and isotherms of the polymers toward a mixture of ten distinct pesticides clearly demonstrate that the adsorbents with a homogeneous open network structure can absorb pesticides via multiple adsorption interactions such as CD inclusion, loading into swelling water and physical adsorption on network. The multivariate regression analysis distinguishes the quantitative contributions of polymer properties to its adsorption potential, among which CD content, swelling capacity and pore size appear to be major influencing factors. Consequently, a facile mixture of three CDPs (i.e., β-CDP, RM-CDP and HP-CDP) was screened to obtain above prerequisite properties. The multiplex polymer could superiorly separate the pesticides at environmentally relevant levels from water.     

Fractional, biodegradable and spectral characteristics of extracted and fractionated sludge extracellular polymeric substances

Correlation between fractional, biodegradable and spectral characteristics of sludge extracellular polymeric substances (EPS) by different protocols has not been well established. This work extracted sludge EPS using alkaline extractants (NH₄OH and formaldehyde + NaOH) and physical protocols (ultrasonication, heating at 80 °C or cation exchange resin (CER)) and then fractionated the extracts using XAD-8/XAD-4 resins. The alkaline extractants yielded more sludge EPS than the physical protocols. However, the physical protocols extracted principally the hydrophilic components which were readily biodegradable by microorganisms. The alkaline extractants dissolved additional humic-like substances from sludge solids which were refractory in nature. Different extraction protocols preferably extracted EPS with distinct fractional, biodegradable and spectral characteristics which could be applied in specific usages.     

Adsorption of lead and humic acid on chitosan hydrogel beads

Chitosan hydrogel beads were studied for the adsorption of lead ions and humic acid from aqueous solutions to examine the adsorption behaviors and mechanisms. The experiments were carried out at room temperature with solution pH ranging from 5 to 7.5 (in near neutral pH range). Three types of batch adsorption experiments, including single species adsorption, sequential adsorption of one species after another and co-adsorption of both species, were investigated. The results show that: (1) adsorption of either species mainly results from the complexations between adsorbate and functional groups at the surface of the hydrogel beads; (2) previously adsorbed species can either act as additional binding sites for, or occupy the same binding sites as the subsequent species to be adsorbed, resulting in enhanced or retarded adsorption of the subsequent species; and (3) for co-adsorption, metal-organic interactions play a very important role in determining the extent of adsorption. It is concluded that multi-species adsorption can be significantly affected by adsorbate interactions and the understanding of these interactions needs great attention in adsorption study in the future.     

Enzymatic extraction of activated sludge extracellular polymers and implications on bioflocculation

This study examines enzyme hydrolysis, a mild, effective, but a rarely used method of extracellular polymer extraction, in removing polymers from mixed culture activated sludge flocs. Two carbohydrate specific enzymes (alpha-amylase and cellulase) and a protein specific enzyme (proteinase) are used during the study. First, the kinetic aspect is investigated, then enzyme dose optimization is carried out on laboratory grown activated sludge samples cultured at solids retention times (SRT) of 4 and 20 days. A more commonly used cation exchange resin (CER) extraction technique is also employed for comparison purposes. Results indicate that the extraction of extracellular polymers by enzymes is a rather quick process reaching equilibrium within only a few hours. As the doses of enzymes are increased, the extracted polymer quantities increase up to a certain dose, beyond which not much extraction is observed. The method does not cause any significant cell lysis as measured by the viable cell counts. Carbohydrate-hydrolyzing enzymes extract small amount of proteins along with the carbohydrates and protein-hydrolyzing enzyme extracts some carbohydrates together with the proteins, indicating that proteins and carbohydrates exist bound to each other in the extracellular polymer network of sludge. Enzyme extraction generally gives a lower estimate of polymers compared to the CER method, but correctly detects the trends in the polymer quantity.     

Emissions of lead and zinc from candles with metal-core wicks

We measured the amount of lead released from 14 different brands of candles with metal-core wicks sold in Michigan. The emissions of lead were found to range from 0.5 to 66 microg/h, and the rates for zinc were from 1.2 to 124 microg/h. It is estimated that burning four of the candles bought in Michigan for 2 h can result in airborne lead concentrations that can pose a threat to human health. In addition to inhalation of lead in the air, children get exposed to lead in candle fumes deposited on the floor, furniture and walls through their hand-to-mouth activity. Burning candles with leaded-core wick may be an important exposure route for lead that has generally been ignored.     

Effect of flow rate and lead/copper pipe sequence on lead release from service lines

A pilot experiment examined lead leaching from four representative configurations of service lines including: (1) 100% lead (Pb), (2) 100% copper (Cu), (3) 50% Pb upstream of 50% Cu, and (4) 50% Pb-downstream of 50% Cu using a range of flow rates. The cumulative mass of lead release indicated that a typical partial replacement configuration (50% lead downstream of copper) did not provide a net reduction in lead when compared to 100% lead pipe (85 mg for 50% Pb-downstream versus 83 mg for 100%-Pb) due to galvanic and deposition corrosion. The partially replaced service line configuration also had a much greater likelihood of producing water with "spikes" of lead particulates at higher flow rates, while tending to produce lower levels of lead at very low flow rates. After the first 214 days the galvanic current between copper and lead was only reduced by 34%, proving that galvanic impacts can be highly persistent even in water with optimized corrosion control by dosing of zinc orthophosphate. Finally, this experiment raises concern about the low flow rates used during some prior home sampling events, which may underestimate exposure to lead during normal water use, especially when galvanic Pb:Cu connections are present.     

Removal of lead from contaminated water bodies using sea nodule as an adsorbent

Adsorption of water soluble lead on polymetallic sea nodule has been studied in detail. Complete decontamination of lead is possible by appropriate sea nodule dosing. Adsorption is also dependent on pH and best adsorption is achieved at pH 6. Beyond pH 6, the desorption of lead from sea nodule surface is practically zero. Residual metal concentrations in the filtrate after adsorption is negligible. Both Freundlich and Langmuir isotherms may reasonably explain adsorption of lead on sea nodule. Chemically bound moisture plays a very crucial role in lead adsorption. Lead adsorptive capability of sea nodule is practically destroyed when calcined at a temperature of 900 degrees C. Lead loading capacity of sea nodule has been estimated at 440 mg of lead per gram of sea nodule. The performance of sea nodule as a lead adsorbent has been successfully tested over six simulated lead contaminated water systems. Lead loading capacity of sea nodule compares favorably with other adsorbents like activated carbon, ion exchange resin, anionic clay, granulated blast furnace slag and natural and treated zeolites.     

Mobilization of arsenic and other naturally occurring contaminants in groundwater of the Main Ethiopian Rift aquifers

This study investigates the mechanisms of arsenic (As) and other naturally occurring contaminants (F⁻, U, V, B, and Mo) mobilization from Quaternary sedimentary aquifers of the Main Ethiopian Rift (MER) and their enrichment in the local groundwater. The study is based on systematic measurements of major and trace elements as well as stable oxygen and hydrogen isotopes in groundwater, coupled with geochemical and mineralogical analyses of the aquifer rocks. The Rift Valley aquifer is composed of rhyolitic volcanics and Quaternary lacustrine sediments. X-ray fluorescence (XRF) results revealed that MER rhyolites (ash, tuff, pumice and ignimbrite) and sediments contain on average 72 wt. % and 65 wt. % SiO₂, respectively. Petrographic studies of the rhyolites indicate predominance of volcanic glass, sanidine, pyroxene, Fe-oxides and plagioclase. The As content in the lacustrine sediments (mean = 6.6 mg/kg) was higher than that of the rhyolites (mean: 2.5 mg/kg). The lacustrine aquifers of the Ziway-Shala basin in the northern part of MER were identified as high As risk zones, where mean As concentration in groundwater was 22.4 ± 33.5 (range of 0.60–190 μg/L) and 54% of samples had As above the WHO drinking water guideline value of 10 μg/L. Field As speciation measurements showed that most of the groundwater samples contain predominantly (∼80%) arsenate-As(V) over arsenite-As(III) species. The As speciation together with field data of redox potential (mean Eh = +73 ± 65 mV) and dissolved-O₂ (6.6 ± 2.2 mg/L) suggest that the aquifer is predominantly oxidative. Water-rock interactions, including the dissolution of volcanic glass produces groundwater with near-neutral to alkaline pH (range 6.9–8.9), predominance of Na–HCO₃ ions, and high concentration of SiO₂ (mean: 85.8 ± 11.3 mg/L). The groundwater data show high positive correlation of As with Na, HCO₃¯, U, B, V, and Mo (R² > 0.5; p < 0.001). Chemical modeling of the groundwater indicates that Fe-oxides and oxyhydroxides minerals were saturated in the groundwater, suggesting that the As reactivity is controlled by adsorption/desorption processes with these minerals. The data show that As and other oxyanion-forming elements such as U, B, Mo, and V had typically higher concentrations at pH > ∼8, reflecting the pH-dependence of their mobilization. Based on the geochemical and stable isotope variations we have established a conceptual model for the occurrence of naturally occurring contaminants in MER groundwater: 1) regional groundwater recharge from the Highland, along the Rift margins, followed by lateral flow and water–rock interactions with the aquifer rocks resulted in a gradual increase of the salinity and naturally occurring contaminants towards the center of the valley; and (2) local δ¹⁸O-rich lake water recharge into adjacent shallow aquifers, followed by additional mobilization of As and other oxyanion-forming elements from the aquifer rocks. We posit that the combined physical-chemical conditions of the aquifers such as oxidizing state, Na–HCO₃ composition, and pH>∼8 lead to enhanced mobilization of oxyanion-forming elements from Fe-oxides and consequently contamination of local groundwater. These geochemical conditions characterize groundwater resources along the Eastern African Rift and thus constitute a potential threat to the quality of groundwater in larger areas of Eastern Africa.