A kinetic study of Cr(VI) reduction by calcium polysulfide

The goal of this study was to determine the influence of pH and oxygen conditions on the reaction kinetics of hexavalent chromium (Cr(VI)) with calcium polysulfide (CPS). The observed kinetic reaction rate, k_obs, between Cr(VI) and CPS was evaluated for the pH range 5.5-8.5, aerobic open, aerobic closed and anaerobic conditions, and two Cr(VI) species (aqueous and adsorbed on goethite). The kinetic model followed a second-order reaction rate, unlike the first-order reaction rate of the Cr(VI)-sulfide reaction. k_obs increased exponentially with pH in the range of 8.5 to 5.5 under anaerobic conditions, while under aerobic conditions k_obs had a maximum at pH 7. Qualitative sulfur analyses showed that thiosulfates were present at and above pH 7 in the aerobic experiments, which can also reduce Cr(VI). Similarly, pure CPS in the presence of oxygen yielded sulfides and thiosulfates, while sulfide converted to a mixture of sulfite, thiosulfates, sulfites and sulfates. CPS is thus likely to have a longer residence time and greater reducing capacity in the subsurface compared to sulfide at neutral and basic pH environments.     

复合填料改性聚硫密封胶的研究

研究轻质碳酸钙或重质碳酸钙、滑石粉、绢云母粉、钛白粉与纳米碳酸钙复合填料对聚硫密封胶(PSS)力学性能的影响.结果表明,填充纳米碳酸钙可提高PSS的拉伸性能.纳米碳酸钙与轻质碳酸钙或重质碳酸钙或滑石粉复合填充则可以提高PSS的拉伸强度;而与云母或钛白粉复合填充时在一定的配比范围内会导致PSS拉伸强度的下降.同时,填料配比对PSS力学性能的影响是非线性的,选择合适的复合填料及其配比才能获得性能良好的PSS.     

Rapid and complete destruction of perchlorate in water and ion-exchange brine using stabilized zero-valent iron nanoparticles

Perchlorate has emerged as a widespread contaminant in groundwater and surface water. Because of the unique chemistry of perchlorate, it has been challenging to destroy perchlorate. This study tested the feasibility of using a new class of stabilized zero-valent iron (ZVI) nanoparticles for complete transformation of perchlorate in water or ion-exchange brine. Batch kinetic tests showed that at an iron dosage of 1.8 g L(-1) and at moderately elevated temperatures (90-95 degrees C), approximately 90% of perchlorate in both fresh water and a simulated ion-exchange brine (NaCl=6% (w/w)) was destroyed within 7h. An activation energy (Ea) of 52.59+/-8.41 kJ mol(-1) was determined for the reaction. Kinetic tests suggested that Cl(VII) in perchlorate was rapidly reduced to chloride without accumulation of any intermediate products. Based on the surface-area-normalized rate constant k(SA), starch- and CMC-stabilized ZVI nanoparticles degraded perchlorate 1.8 and 3.3 times, respectively, faster than non-stabilized ZVI particles. Addition of a metal catalyst (Al, Cu, Co, Ni, Pd, or Re) did not show any reaction improvement. This technology provides an effective method for complete destruction of perchlorate in both contaminated water and brine.     

A novel approach to calcium removal from calcium-rich industrial wastewater

Calcium-rich wastewater is a problem for industries due to calcification during downstream processing. The potential for Ca2+ removal from industrial wastewater through ureolytic microbiological carbonate precipitation was investigated for the first time. Batch experiments were used to determine feasible urea concentrations and hydraulic retention times. These results were applied in a semi-continuous reactor system, where the emphasis was placed on the development of a calcifying sludge. Calcium removal in excess of 90% was achieved throughout the experimental period, while the effluent pH remained at a reasonable level.     

Chromium removal by combining the magnetic properties of iron oxide with adsorption properties of carbon nanotubes

The adsorption features of multiwall carbon nanotubes (MWCNTs) with the magnetic properties of iron oxides have been combined in a composite to produce a magnetic adsorbent. Composites of MWCNT/nano-iron oxide were prepared, and were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and Fourier transform infrared spectroscopy (FTIR). XRD suggests that the magnetic phase formed is maghemite and/or magnetite. FESEM image shows nano-iron oxides attached to a network of MWCNTs. The adsorption capability of the composites was tested in batch and fixed bed modes. The composites have demonstrated a superior adsorption capability to that of activated carbon. The results also show that the adsorptions of Cr(III) on the composites is strongly dependent on contact time, agitation speed and pH, in the batch mode; and on flow rate and the bed thickness in the fixed bed mode. Along with the high surface area of the MWCNTs, the advantage of the magnetic composite is that it can be used as adsorbent for contaminants in water and can be subsequently controlled and removed from the medium by a simple magnetic process.     

Removal of charged micropollutants from water by ion-exchange polymers - Effects of competing electrolytes

A wide variety of environmental compounds of concern, e.g. pharmaceuticals or illicit drugs, are acids or bases that may predominantly be present as charged species in drinking water sources. These charged micropollutants may prove difficult to remove by currently used water treatment steps (e.g. UV/H₂O₂, activated carbon (AC) or membranes). We studied the sorption affinity of some ionic organic compounds to both AC and different charged polymeric materials. Ion-exchange polymers may be effective as additional extraction phases in water treatment, because sorption of all charged compounds to oppositely charged polymers was stronger than to AC, especially for the double-charged cation metformin. Tested below 1% of the polymer ion-exchange capacity, the sorption affinity of charged micropollutants is nonlinear and depends on the composition of the aqueous medium. Whereas oppositely charged electrolytes do not impact sorption of organic ions, equally charged electrolytes do influence sorption indicating ion-exchange (IE) to be the main sorption mechanism. For the tested polymers, a tenfold increased salt concentration lowered the IE-sorption affinity by a factor two. Different electrolytes affect IE with organic ions in a similar way as inorganic ions on IE-resins, and no clear differences in this trend were observed between the sulphonated and the carboxylated cation-exchanger. Sorption of organic cations is five fold less in Ca²⁺ solutions compared to similar concentrations of Na⁺, while that of anionic compounds is three fold weaker in SO₄^2- solutions compared to equal concentrations of Cl⁻.     

Ammonia removal from wastewater by ion exchange in the presence of organic contaminants

The scope of this study was the removal of ammonium by ion exchange from simulated wastewater. The study looks at the effect of organics upon ammonium ion exchange equilibrium uptake. The ion exchangers included a natural zeolite clinoptilolite, and two polymeric exchangers, Dowex 50w-x8, and Purolite MN500. The organic compounds studied included citric acid and a number of proteins. The traditional method for removal of ammonium and organic pollutants from wastewater is biological treatment, but ion exchange offers a number of advantages including the ability to handle shock loadings and the ability to operate over a wider range of temperatures. The results show that in most of the cases studied, the presence of organic compounds enhances the uptake of ammonium ion onto the ion exchangers.     

Pesticides removal from waste water by activated carbon prepared from waste rubber tire

Waste rubber tire has been used for the removal of pesticides from waste water by adsorption phenomenon. By applying successive chemical and thermal treatment, a basically cabonaceous adsorbent is prepared which has not only a higher mesopore, macropore content but also has a favorable surface chemistry. Presence of oxygen functional groups as evidenced by FTIR spectra along with excellent porous and surface properties were the driving force for good adsorption efficiency observed for the studied pesticides: methoxychlor, methyl parathion and atrazine. Batch adsorption studies revealed maximum adsorption of 112.0 mg g⁻¹, 104.9 mg g⁻¹ and 88.9 mg g⁻¹ for methoxychlor, atrazine and methyl parathion respectively occurring at a contact time of 60 min at pH 2 from an initial pesticide concentration of 12 mg/L. These promising results were confirmed by column experiments; thereby establishing the practicality of the developed system. Effect of various operating parameters along with equilibrium, kinetic and thermodynamic studies reveal the efficacy of the adsorbent with a higher adsorption capacity than most other adsorbents. The adsorption equilibrium data obey Langmuir model and the kinetic data were well described by the pseudo-first-order model. Applicability of Bangham’s equation indicates that diffusion of pesticide molecules into pores of the adsorbent mainly controls the adsorption process. Spontaneous, exothermic and random characteristics of the process are confirmed by thermodynamic studies. The developed sorbent is inexpensive in comparison to commercial carbon and has a far better efficiency for pesticide removal than most other adsorbents reported in literature.     

Arsenic removal from high-arsenic water by enhanced coagulation with ferric ions and coarse calcite

Arsenic removal from high-arsenic water in a mine drainage system has been studied through an enhanced coagulation process with ferric ions and coarse calcite (38-74 microm) in this work. The experimental results have shown that arsenic-borne coagulates produced by coagulation with ferric ions alone were very fine, so micro-filtration (membrane as filter medium) was needed to remove the coagulates from water. In the presence of coarse calcite, small arsenic-borne coagulates coated on coarse calcite surfaces, leading the settling rate of the coagulates to considerably increase. The enhanced coagulation followed by conventional filtration (filter paper as filter medium) achieved a very high arsenic removal (over 99%) from high-arsenic water (5mg/l arsenic concentration), producing a cleaned water with the residual arsenic concentration of 13 microg/l. It has been found that the mechanism by which coarse calcite enhanced the coagulation of high-arsenic water might be due to attractive electrical double layer interaction between small arsenic-borne coagulates and calcite particles, which leads to non-existence of a potential energy barrier between the heterogeneous particles.     

Selective removal of phosphorus from wastewater combined with its recovery as a solid-phase fertilizer

Influx of Phosphorus (P) into freshwater ecosystems is the primary cause of eutrophication which has many undesirable effects. Therefore, P discharge limits for effluents from WWTPs is becoming increasingly common, and may be as low as 10 μg/L as P. While precipitation, filtration, membrane processes, Enhanced Biological Phosphorus Removal (EBPR) and Physico-chemical (adsorption based) methods have been successfully used to effect P removal, only adsorption has the potential to recover the P as a usable fertilizer. This benefit will gain importance with time since P is a non-renewable resource and is mined from P-rich rocks. This article provides details of a process where a polymeric anion exchanger is impregnated with iron oxide nanoparticles to effectuate selective P removal from wastewater and its recovery as a solid-phase fertilizer. Three such hybrid materials were studied: HAIX, DOW-HFO, & DOW-HFO-Cu. Each of these materials combines the durability, robustness, and ease-of-use of a polymeric ion-exchanger resin with the high sorption affinity of Hydrated Ferric Oxide (HFO) toward phosphate. Laboratory experiments demonstrate that each of the three materials studies can selectively remove phosphate from the background of competing anions and phosphorus can be recovered as a solid-phase fertilizer upon efficient regeneration of the exchanger and addition of a calcium or magnesium salt in equimolar (Ca/P or Mg/P) ratio. Also, there is no leaching of Fe or Cu from any of these hybrid exchangers.     

Removal and recovery of Cr(VI) from polluted ground waters: a comparative study of ion-exchange technologies

The focus of this work has been the study of Cr(VI) removal from ground waters and the simultaneous concentration for its reuse using three different technological alternatives: anion-exchange resins, liquid-liquid extraction assisted by hollow fibre membranes and emulsion pertraction. The viability of the considered objectives, i.e., Cr(VI) separation (<0.5 g/m3) and concentration for reuse (>20,000 g/m3) has been checked and a comparative analysis of the three technologies has been performed. Although the flexibility and ease of operation of non-dispersive solvent extraction, anion-exchange resins and emulsion pertraction lead to higher velocities of chromium removal, yet still maintaining similar concentration efficiencies.     

Improvement of desalination efficiency in capacitive deionization using a carbon electrode coated with an ion-exchange polymer

A composite carbon electrode coated with a cation-exchange polymer, crosslinked poly(vinyl alcohol) with sulfosuccinic acid, was fabricated to enhance the desalination performance of a capacitive deionization (CDI) system. The electrochemical properties of the prepared electrode were characterized by impedance spectroscopy, and desalination experiments were carried out at various operating conditions using a CDI cell with carbon electrodes only, and a membrane-capacitive-deionization (MCDI) cell including a coated-carbon electrode, to evaluate the effect of the coated-carbon electrode on desalination performance. The electrical resistance of the coated electrode was increased by a small amount over the uncoated electrode, but the capacitance was improved by the coating. In the CDI cell, the salt-removal efficiencies were in the range of 50-67%, while the efficiencies increased to 75-85% for the MCDI cell. Depending on the operating conditions, the salt-removal and current efficiencies of the MCDI cell were enhanced by 27-56% and 69-95%, respectively, compared to the CDI cell. The enhanced efficiency for the MCDI cell was attributed to the selective transport of cations between the electrode surface and bulk solution due to the cation-exchange coating layer.     

Electrochemical removal of chromium from wastewater by using carbon aerogel electrodes

A study has been carried out to determine the feasibility of electrochemical removal of chromium ions from industrial wastewater using carbon aerogel electrodes. In this work the effect of key variables including pH (2-7), concentration 2-8 (mg/l), and charge 0.3-1.3 (A h) was determined. The metal ion removal was significantly increased at reduced pH and high charge conditions. The metal concentration in the wastewater can be reduced by 98.5% under high charge (0.8A h) and acidic conditions (pH 2). The effect of the independent parameters--pH, effluent concentration and charge on the percentage removal was depicted by a quadratic equation obtained using Box-Behnken model. The regression analysis gave a R2 value of 0.9469 shows a close fit between the experimental results and the model predictions. The model was further used to optimise the parameters to maximise the percentage Cr-removal to more than 98%.     

Modelling biological and chemically induced precipitation of calcium phosphate in enhanced biological phosphorus removal systems

The biologically induced precipitation processes can be important in wastewater treatment, in particular treating raw wastewater with high calcium concentration combined with Enhanced Biological Phosphorus Removal. Currently, there is little information and experience in modelling jointly biological and chemical processes. This paper presents a calcium phosphate precipitation model and its inclusion in the Activated Sludge Model No 2d (ASM2d). The proposed precipitation model considers that aqueous phase reactions quickly achieve the chemical equilibrium and that aqueous-solid change is kinetically governed. The model was calibrated using data from four experiments in a Sequencing Batch Reactor (SBR) operated for EBPR and finally validated with two experiments. The precipitation model proposed was able to reproduce the dynamics of amorphous calcium phosphate (ACP) formation and later crystallization to hydroxyapatite (HAP) under different scenarios. The model successfully characterised the EBPR performance of the SBR, including the biological, physical and chemical processes.     

Model experiments on the microbial removal of chromium from contaminated groundwater

A bacterial consortium with representatives of sulfate-reducing and denitrifying bacteria was selectively enriched. Model experiments under microaerobic conditions showed that it precipitated chromium from Cr (VI)-containing waters (area of a former electroplating factory, Leipzig, Germany) by two different mechanisms: by sulfate reduction and precipitation as sulfide, and by some direct reduction. Sulfate reduction needed fatty acids as organic substrates and resulted at the first stage in no sulfide accumulation. In the absence of the fatty acids but with straw as organic substrate, the direct reduction of chromium was observed without sulfate reduction. In this case Cr (VI)-reduction rate correlated with that of the denitrification.     

Enhanced arsenite removal from water by Ti(SO4)2 coagulation

Coagulation with the conventional coagulants such as ferric and aluminum salts is not efficient for As(III) removal. In this study Ti(SO₄)₂ was employed for enhanced As(III) removal and Fe₂(SO₄)₃ was used as a reference. The removal efficiencies of As(III) by Ti(SO₄)₂ at pH 4.0–9.0 were greater than that by Fe₂(SO₄)₃ by 7.39–32.8% and 3.14–48.1% for coagulants dosed at 8.0 mg/L and 12.0 mg/L, respectively. The advantage of Ti(SO₄)₂ over Fe₂(SO₄)₃ for As(III) removal was more significant at lower pH, which may be ascribed to the more negatively charged surface of Ti(IV) hydroxides. To reduce As(III) from 0.2 mg/L to 10 μg/L, the necessary dosage of Ti(SO₄)₂ was only ～50% of that of Fe₂(SO₄)₃. The adsorption capacity of As(III) on Ti(IV) hydroxides formed in-situ was greater than that on Fe(III) hydroxides formed in-situ by ～100 mg/g and several times higher than the adsorption capacities of TiO₂ for As(III) reported in the literature. The presence of competing anions, silicate, phosphate and humic acid, did not alter the advantage of Ti(SO₄)₂ over Fe₂(SO₄)₃ for arsenite removal. Replacing partial Ti(SO₄)₂ with Fe₂(SO₄)₃ (same dosage) and applying them sequentially could achieve similar As(III) removal efficiency as single Ti(SO₄)₂, which could thus reduce the chemical cost. The extended X-ray absorption fine structure (EXAFS) spectroscopy indicated that As(III) form bidentate binuclear surface complexes with Ti(IV) hydroxides as evidenced by As(III)-Ti bond distances of 3.33–3.35 Å. This study revealed that Ti(SO₄)₂ may be an alternative coagulant for efficient As(III) removal.     

Simultaneous colour and DON removal from sewage treatment plant effluent: Alum coagulation of melanoidin

The aim of this study was to detect and characterise melanoidin in sewage treatment plant (STP) effluent, and to study the ability of alum coagulation to remove the colour and dissolved organic nitrogen (DON) associated with melanoidin. The melanoidin is non-biodegradable due to the complex cyclic based structure and thus it directly contributes to effluent nitrogen concentrations from the sewage treatment plant (STP). Lowering of effluent total nitrogen limits and the link between colour and chlorinated disinfection by-products have therefore driven a need to understand the structure, properties and treatability of DON species found in STP effluent.The focus of this paper is the refractory coloured, organic nitrogen compound melanoidin. Wetalla STP effluent has relatively high colour (170 mg-PtCo L⁻¹) and DON (2.5 mg L⁻¹) for a biological nutrient removal STP, owing to an industrial supply of melanoidin containing molasses fermentation wastewater. Alum coagulation jar tests were performed on synthetic melanoidin solution, STP effluent containing melanoidin (Wetalla, Toowoomba, Australia) and STP effluent free of melanoidin (Merrimac, Gold Coast, Australia) to examine the treatability of melanoidin and its associated colour and DON content when present in STP effluent.The removal of melanoidin from STP effluent resulted in significant colour and DON reduction. An alum dose of 30 mg L⁻¹ as aluminium was sufficient to reach maximum removal of colour (75%), DON (42%) and dissolved organic carbon (DOC) (30%) present in melanoidin containing STP effluent. Alum was shown to preferentially remove DON with a molecular weight >10 kDa over small molecular weight DON. Fluorescence excitation-emission matrix examination of the humic compounds present in the STP effluent indicated that melanoidin type humic compounds were more readily removed by alum coagulation than other humic compounds.     

Properties of geosynthetics exhumed from a final cover at a solid waste landfill

Samples of geocomposite drain (GCD), geomembrane (GM), and geosynthetic clay liner (GCL) were exhumed from a final cover at a solid waste landfill to assess their condition after 4.7–5.8 yr of service. Permittivity of the GCD diminished by a factor of 3.9, but the transmissivity was higher than published by the manufacturer. Ply adhesion of the GCD diminished by a factor of 2.0. Geonet ribs in the geocomposite drain (GCD) contained a light coating of fines and plant roots, but there was no evidence of significant clogging. The geotextile on the upper surface of the GCD met the commonly used criterion for filtration (AOS < 0.6 mm for adjacent soil with <50% fines), indicating that this filtration criterion was satisfactory. Tensile yield strength of the GM diminished by a factor of 1.2, but the melt flow index was unchanged and the oxidation induction time exceeded the manufacturer's specification. GCD-geomembrane interface strength appeared unchanged. Four GCL samples had hydraulic conductivities 1000–10,000 times higher than the hydraulic conductivity measured during construction, whereas hydraulic conductivity of the other seven samples was practically unchanged. Based on these observations, the following reduction factors are suggested for installation damage and near-term service conditions (<6 yr) for the geosynthetics used at this site: GCD permittivity or transmissivity – 4.0, GCD ply adhesion – 2.0, geomembrane tensile strength – 1.5, and GCD-geomembrane interface friction – 1.0. No recommendation is made regarding a factor for the hydraulic conductivity of GCLs.     

Rapid and economical indicator for evaluating arsenic removal with minimum aluminum residual during coagulation process

Detection of various types of contaminants in water treatment plant by sophisticated analytical methods such as inductively coupled plasma/mass spectrometry and gas chromatography/mass spectrometry requires hours to days to provide the results. Because naturally occurring ultraviolet (UV) active compounds are commonly present in almost all source waters and can be rapidly monitored by UV absorbance at 260 nm (E260), the extent of correlation between the removal efficiency of E260 and the removal efficiency of As(V) with minimum soluble residual Al by coagulation process was investigated. Percentage removals for E260 were well correlated to those of As(V). When sufficient alum or polyaluminum chloride (PACl) was added for 60-65% removal of E260, 90-95% removal of As(V) was achieved with minimum soluble residual Al regardless of the initial level of turbidity, E260, and As(V). As E260 analysis is precisely available even by an unskilled plant operator in a few minutes, E260 removal efficiency appears to be the promising economical indicator for monitoring the effectiveness of the coagulation process for the removal of contaminants with minimum residual Al.     

Characterisation of the impact of coagulation and anaerobic bio-treatment on the removal of chromophores from molasses wastewater

The performance of a coagulation sequence using aluminium chlorohydrate (ACH) and a low MW polydiallyldimethylammonium chloride (polyDADMAC), and ferric chloride, for decolourising a high-strength industrial molasses wastewater was compared at bench scale. At their optimum dosages, ACH/polyDADMAC gave higher colour removal than FeCl₃ (45% cf. 28%), whereas COD reduction was similar (∼30%), indicating preferential removal of melanoidins (a major contributor to the colour) by ACH/polyDADMAC. Size exclusion chromatography and fluorescence excitation-emission matrix spectrometry suggested that chromophoric Fe-organic complexes were formed during FeCl₃ treatment of the molasses wastewater, which appeared to compromise decolourisation efficiency. Anaerobic bio-treatment of the wastewater enhanced the coagulation efficiency markedly, with FeCl₃ achieving 94% colour and 96% COD removal, while ACH/polyDADMAC gave 70% and 56% removal, respectively. The improved decolourisation was attributed to the decrease in low MW organics (<500 Da) and biopolymers by the biological treatment, leading to reduced competition with melanoidins for interaction with coagulant/flocculant. For both the wastewater and the biologically treated wastewater, ACH/polyDADMAC treatment gave flocs with markedly better settling properties compared with FeCl₃.