Direct Determination of Absolute Radical Quantum Yields in Hydroxyl and Sulfate Radical-Based Treatment Processes.

The absolute radical quantum yield (Φ) is a critical parameter to evaluate the efficiency of radical-based processes in engineered water treatment. However, measuring Φ is fraught with challenges, as current quantification methods lack selectivity, specificity, and anti-interference capabilities, resulting in significant error propagation. Herein, we report a direct and reliable time-resolved technique to determine Φ at pH 7.0 for commonly used radical precursors in advanced oxidation processes. For H2O2 and peroxydisulfate (PDS), the values of Φ•OH and ΦSO4•- at 266 nm were measured to be 1.10 ± 0.01 and 1.46 ± 0.05, respectively. For peroxymonosulfate (PMS), we developed a new approach to determine Φ•OHPMS with terephthalic acid as a trap-and-trigger probe in the nonsteady state system. For the first time, the Φ•OHPMS value was measured to be 0.56 by the direct method, which is stoichiometrically equal to ΦSO4•-PMS (0.57 ± 0.02). Additionally, radical formation mechanisms were elucidated by density functional theory (DFT) calculations. The theoretical results showed that the highest occupied molecular orbitals of the radical precursors are O-O antibonding orbitals, facilitating the destabilization of the peroxy bond for radical formation. Electronic structures of these precursors were compared, aiming to rationalize the tendency of the Φ values we observed. Overall, this time-resolved technique with specific probes can be used as a reliable tool to determine Φ, serving as a scientific basis for the accurate performance evaluation of diverse radical-based treatment processes.

Performance, microbial community and inhibition kinetics of long-term Cu2+ stress on an air-lift nitritation reactor with self-recirculation.

Biological nitrogen removal process could be affected due to the presence of heavy metals owing to their toxicity and accumulation in the sludge. In this study, the impact of Cu2+ shock on a long-term nitritation operation was investigated in an air-lift reactor with self-recirculation. Both the dynamics of microbial community and inhibition kinetics under Cu2+ stress were ascertained. The results showed that Cu2+ exerted severe inhibition on nitritation performance of an air-lift reactor (ALR) at 25 mg/L. The corresponding NH4+-N removal efficiency decreased to below 50%, which was mainly due to the variation of microbial community structure, especially the inhibition of nitrifiers like Nitrosomonas (the relative abundance decreased from 30% to 1% after Cu2+ inhibition). Kinetic parameters were obtained and compared after fitting the Haldane model. The long-term Cu2+ stress on the ALR aggravated the ammonium affinity and the resistance to substrate self-inhibition of the nitritation sludge, but reduced the resistance to Cu2+ inhibition. Furthermore, Cu2+ acted as uncompetitive inhibitor on nitritation process. Our results provide new insights into the nitritation characteristics under long-term Cu2+ stress.

Mechanistic Study on the Role of Soluble Microbial Products in Sulfate Radical-Mediated Degradation of Pharmaceuticals.

The role of soluble microbial products (SMP), the most important component of effluent organic matter from municipal wastewater treatment plants, in sulfate radical (SO4•-)-based advanced oxidation technologies (AOTs) remains substantially unclear. In this study, we first utilized a suite of macro- and microanalytical techniques to characterize the SMP from a membrane bioreactor for its fundamental molecular, spectroscopic, and reactivity properties. The degradation kinetics of three representative pharmaceuticals (i.e., naproxen, gemfibrozil, and sulfadiazine) in the presence of SMP was significantly reduced as compared to in its absence. Possible mechanisms for the interference by SMP in degrading these target compounds (TCs) were investigated. The low percentage of bound TCs to SMP ruled out the cage effect. The measurement of steady-state 1O2 concentration indicated that formation of 1O2 upon UV irradiation on SMP was not primarily responsible for the degradation of TCs. However, the comparative and quenching results reveal that SMP absorbs UV light acting as an inner filter toward the TCs, and meanwhile scavenges SO4•- with a high second-order rate constant of 2.48 × 108 MC-1 s-1.

Short-term effects of nanoscale Zero-Valent Iron (nZVI) and hydraulic shock during high-rate anammox wastewater treatment.

The stability and resilience of an anaerobic ammonium oxidation (anammox) system under transient nanoscale Zero-Valent Iron (nZVI) (50, 75 and 100 mg L-1), hydraulic shock (2-fold increase in flow rate) and their combination were studied in an up-flow anaerobic sludge blanket reactor. The response to the shock loads can be divided into three phases i.e. shock, inertial and recovery periods. The effects of the shock loads were directly proportional to the shock intensity. The effluent quality was gradually deteriorated after exposure to high nZVI level (100 mg L-1) for 2 h. The higher effluent sensitivity index and response caused by unit intensity of shock was observed under hydraulic and combined shocks. Notably, the specific anammox activity and the content of heme c were considerably reduced during the shock phase and the maximum loss rates were about 30.5% and 24.8%, respectively. Nevertheless, the extracellular polymeric substance amount in the shock phase was enhanced in varying degrees and variation tendency was disparate at all the tested shock loads. These results suggested that robustness of the anammox system was dependent on the magnitude shocks applied and the reactor resistance can be improved by reducing hydraulic retention time with the increase of nZVI concentration under these circumstances.

Enhanced short-cut nitrification in an airlift reactor by CaCO3 attachment on biomass under high bicarbonate condition.

The short-cut nitrification (SCN) performance of an airlift reactor (ALR) was investigated under increasing bicarbonate condition. The sequential increase of bicarbonate from 2.5 to 7.0 g/L accelerated the nitrite accumulation and improved the NAP to 99 %. With the increase of bicarbonate dose to 11 g/L, the ammonium removal efficiency and the ammonium removal rate (ARR) were improved to 95.1 % and 0.57 kg/m(3)/day, respectively. However, the elevation of bicarbonate concentration from 11.0 to 14.0 g/L gradually depreciated the nitrite accumulation percentage to 62.5 %. Then, the reactor was operated in increasing ammonium strategy to increase the nitrogen loading rate (NLR) to 1.1 kg/m(3)/day under 700 mg/L influent ammonium concentration. The ARR and nitrite production rate were elevated to 1.1 and 0.9 kg/m(3)/day, respectively. The SCN performance was improved to 1.8 kg/m(3)/day (NLR) by the subsequent progressive shortening of HRT to 4.8 h at ammonium concentration of 350 mg/L, which was 1.6 times higher than that of the increasing ammonium strategy. Chemical analysis with EDS, FTIR and XRD confirmed the presence of CaCO3 precipitates on biomass surface during the long-term operation under high bicarbonate conditions. The attachment of precipitates to the SCN sludge helped to improve the biomass settleability and finally enhanced the SCN performance of the ALR.

Co-treatment of gypsum sludge and Pb/Zn smelting slag for the solidification of sludge containing arsenic and heavy metals.

Wastewater treatment sludge from a primary lead-zinc smelter is characterized as hazardous waste and requires treatment prior to disposal due to its significant arsenic and heavy metals contents. This study presents a method for the stabilization of arsenic sludge that uses a slag based curing agent composed of smelting slag, cement clinker and limestone. The Unconfined Compressive Strength (UCS) test, the China Standard Leaching Test (CSLT), and the Toxicity Characteristic Leaching Procedures (TCLP) were used to physically and chemically characterize the solidified sludge. The binder ratio was determined according to the UCS and optimal experiments, and the optimal mass ratio of m (smelting slag): m (cement clinker): m (gypsum sludge): m (limestone) was 70:13:12:5. When the binder was mixed with arsenic sludge using a mass ratio of 1:1 and then maintained at 25 °C for 28 d, the UCS reached 9.30 MPa. The results indicated that the leached arsenic content was always less than 5 mg/L, which is a safe level, and does not contribute to recontamination of the environment. The arsenic sludge from the Zn/Pb metallurgy plant can be blended with cement clinker and smelting slag materials for manufacturing bricks and can be recycled as construction materials.

Depolymerization and decolorization of kraft lignin by bacterium Comamonas sp. B-9.

There is no commercial or industrial-scale process for the remediation of black liquor using microorganisms to date. One of the most important causes is that most microorganisms are not able to use lignin as their principal metabolic carbon or energy source. The bacterial strain Comamonas sp. B-9 has shown remarkable ability to degrade kraft lignin and decolorize black liquor using lignin as its principal metabolic carbon and energy source. This report looks at the depolymerization and decolorization of kraft lignin by Comamonas sp. B-9. The degradation, decolorization, and total carbon removal reached 45, 54, and 47.3%, respectively, after 7 days treatment. Comamonas sp. B-9 was capable of depolymerizing kraft lignin effectively as analyzed by gel permeation chromatography and decolorization via degrading benzene ring structures as shown using Fourier transform infrared spectroscopy analysis.

[Start-up and Recovery Performance of ANAMMOX Reactors Under Long-term Starvation].

The application of ANAMMOX technology is constrained by sluggish growth and difficulty in enriching ANAMMOX bacteria. Long-term starvation of functioning bacteria due to limited substrate supply makes the steady operation of ANAMMOX reactors more difficult. Re-examining the start-up and recovery performance of the ANAMMOX reactor and identifying its resistance mechanism are important from the standpoint of long-term starvation. By inoculating nitrifying and denitrifying sludge under various operating circumstances, the ANAMMOX reactors were successfully started. Under various start-up procedures, the tolerance mechanism and recovery performance were examined. The outcomes demonstrated that the denitrifying sludge-inoculated reactor operated steadily with a high substrate concentration and low flow rate. After 85 days of operation, the removal efficiencies of NH4+-N, NO2--N, and total nitrogen reached 98.7%, 99.3%, and 89.3%, respectively. After 144 days of starvation and 30 days of recovery, the better nitrogen removal performance was achieved at a low substrate concentration and high flow rate, and the removal efficiencies were 99.8% （NH4+-N）, 99.8% （NO2--N）, and 93.6% （total nitrogen）. During the starvation, extracellular polymeric substances wrapped the ANAMMOX bacteria and kept them intact to resist long-term starvation stress. The expression of nirS, hzsA, and hdh genes ensured the synthesis of nitrite/nitric oxide oxidoreductase, hydrazine synthase, and hydrazine dehydrogenase to maintain ANAMMOX activity. There was no significant difference in the relative abundance of ANAMMOX bacteria before and after starvation recovery. Candidatus Kuenenia had better anti-hunger ability, and the relative abundance increased by more than 86% after 30 days of recovery, confirming its tolerance to long-term starvation.

Characterization of the microplastic photoaging under the action of typical salt ions of biological nitrogen removal processes.

Microplastics (MPs) are one of the most prevalent and diverse contaminants, and wastewater treatment plants are significant MP aggregators. Controlling the pollution caused by microplastics requires an understanding of how they age. The properties of the MPs photoaging process under the influence of salt ions typical of biological nitrogen elimination processes were disclosed in this work. The aging process of polyvinyl chloride microplastics (PVC-MPs) was greatly slowed down by greater HCO3- and NO2- concentrations, according to a comparison of the carbonyl index changes that occurred during photoaging. The carbonyl index had a negative correlation with the thermal stability of the photo-aged PVC-MPs, and aging accelerated the elimination of chlorine from the water. The samples were aged by UV radiation after 36 h at 40 °C, and the amount of chlorine eliminated was 10.13 times greater than that of the original MPs samples. It was discovered that the leachate concentration of aged MPs dramatically increased with decreasing particle size and was positively connected with the level of aging by comparing the concentration of leachate for two particle sizes (1 mm and 100 m). Photoaging caused MPs to become rougher, which in turn improved the NO3--N, NH4+-N, and NO2--N adsorption by PVC-MPs.

Electrochemically selective ammonium recovery from wastewater via coupling hydrogen bonding and charge storage.

Electrochemical ammonium (NH4+) storage (EAS) has been established as an efficient technology for NH4+ recovery from wastewater. However, there are scientific difficulties unsolved regarding low storage capacity and selectivity, restricting its extensive engineering applications. In this work, electrochemically selective NH4+ recovery from wastewater was achieved by coupling hydrogen bonding and charge storage with self-assembled bi-layer composite electrode (GO/V2O5). The NH4+ storage was as high as 234.7 mg N g-1 (> 102 times higher than conventional activated carbon). Three chains of proof were furnished to elucidate the intrinsic mechanisms for such superior performance. Density functional theory (DFT) showed that an excellent electron-donating ability for NH4+ (0.08) and decrease of diffusion barrier (22.3 %) facilitated NH4+ diffusion onto electrode interface. Physio- and electro-chemical results indicated that an increase of interlamellar spacing (14.3 %) and electrochemical active surface area (ECSA, 388.9 %) after the introduction of GO were responsible for providing greater channels and sites toward NH4+ insertion. Both non-ionic chemical-bonding (V5+=O‧‧‧H, hydrogen-bonding) and charge storage were contributed to the higher capacity and selectivity for NH4+. This work offers underlying guideline for exploitation a storage manner for NH4+ recovery from wastewater.

Enhanced remediation of black liquor by activated sludge bioaugmented with a novel exogenous microorganism culture.

Black liquor (BL) is a notoriously difficult wastewater to treat due to the economic and efficiency limitations of physiochemical methods and intrinsic difficulties with bioremediation strategies caused by the high pH (10-13) and lignin content. This study investigated the feasibility of a novel bioaugmentation strategy for BL treatment, which uses a mixed microorganism culture of lignocellulose-degrading microorganisms isolated from degraded bamboo slips. Black liquor treatment was assessed in terms of chemical oxygen demand (COD) and color removal with a sequencing batch reactor organic loading rate of 9 kg COD/L·day under highly alkaline conditions (pH 10). Results revealed that bioaugmented activated sludge treatment of BL with special mixed microorganisms significantly enhanced the removal efficiency of COD, color, and lignin from the wastewater up to 64.8, 50.5, and 53.2 %, respectively. Gel permeation chromatography profiles showed that the bioaugmentation system could successfully degrade high molecular lignin fragments in black liquor. This work confirms bioaugmentation as a feasible alternative strategy for enhanced biological treatment of wastewater with high lignin content and high organic load rate under strongly alkaline conditions.

Dosing with pyrite significantly increases anammox performance: Its role in the electron transfer enhancement and the functions of the Fe-N-S cycle.

Anaerobic ammonium oxidation (anammox) represents an energy-efficient process for biological nitrogen removal from ammonium-rich wastewater. However, there are mechanistic issues unsolved regarding the low microbial electron transfer and undesired accumulation of nitrate in treated water, limiting its widespread engineering applications. We found that the addition of pyrite (1 g L-1 reactor), an earth-abundant iron-bearing sulfide mineral, to the anammox system significantly improved the nitrogen removal rate by 52% in long-term operation at a high substrate shock loading (3.86 kg N m-3 d-1). Two lines of evidence were presented to unravel the underlying mechanisms of the pyrite-induced enhancement. Physiochemical evidence indicated that an increase of cytochromes c and Fe-S protein was responsible for the accelerated electron transfer among metabolic enzymes. Multi-omics evidence showed that the depletion of nitrate was attributed to the Fe-N-S cycle driven by nitrate-dependent Fe(II) oxidation and S-based denitrification. This study deepens our understanding of the roles of electron transfer and the Fe-N-S cycle in anammox systems, providing a fundamental basis for the development of mediators in the anammox process for practical implications.

[Removal Characteristics of Four Typical Antibiotics in Denitrification System].

Wastewater treatment plants are an important gathering place for antibiotics, where denitrification plays a vital role in biological nitrogen removal. In order to explore the removal characteristics of antibiotics in a denitrifying sludge system, norfloxacin (NOR), oxytetracycline (OTC), sulfamethoxazole (SMX), and trimethoprim (TMP) were selected to investigate their transformation under different carbon source conditions in a denitrification system. The contribution of adsorption and biodegradation for antibiotic removal was also evaluated in this study. The results showed that a certain proportion of NOR, OTC, and TMP could be removed by denitrification, whereas NOR and OTC could act as the sole carbon source for denitrification. The removal of NOR and OTC showed a rapid adsorption and then slow biodegradation trend in the denitrification system. The contributions of adsorption were recorded as 83.5% and 58.9% for NOR and OTC removal, respectively. More than 40% were adsorbed by extracellular polymer substances (EPS), whereas the P450 enzyme played an important role in the OTC biodegradation process, with a contribution of 20%.

Distinct membrane fouling characteristics of anammox MBR with low NO2--N/NH4+-N ratio.

The bacterial growth and death, and extracellular polymeric substances (EPS) and soluble microbial products (SMP) in aerobic membrane bioreactor (MBR) cause severe membrane fouling. Anammox bacteria grow slowly but produce much EPS and SMP. Therefore, the membrane fouling characteristic of anammox MBR is still indistinct. A NO2--N/NH4+-N < 1.0 into in the influent of an anammox MBR applies to investigate: 1) the slowest growing anammox bacteria (Candidatus Jettenia) could be enriched or not; 2) its membrane fouling characteristic. Results showed that Candidatus Jettenia successfully accumulated from 0.01% to 26.19%. The fouling characteristic of anammox MBR was entirely different from other MBRs. Firstly, obvious low transmembrane pressure (<4 KPa, 125 days) and low amount of foulants (0.22 gVSS/m2) might result from N2 production and the slow-growing Candidatus Jettenia. Secondly, the analysis of the components of membrane foulants indicated that polysaccharides of SMP in the gel layer and pore foulants were the key factors affecting membrane fouling. Finally, the large particle size of foulants (200 µm) might be caused by anammox bacteria living inside the foulants under anaerobic conditions. This study provides systematic insights into membrane characteristics of anammox MBR and a basis for the enrichment of anammox bacteria by MBR.

Understanding the slight inhibition of high As(III) stress on nitritation process: Insights from arsenic speciation and microbial community analyses.

Nitritation process with ammonia-oxidizing bacteria frequently suffers inhibition from heavy metals in industrial wastewater treatment. However, As(III), one of the most toxic metalloids, showed slight inhibition though the arsenic accumulation content in the sludge reached 91.8 mg L-1 in this study. Here, we combined long-term reactor operation with microbiological analyses to explore the slight inhibition mechanisms of As(III) on nitritation consortia. The results showed that no obvious changes induced by As(III) occurred in apparent characteristics and morphology of the nitritation consortia, whereas dosing As(III) induced shifts in the arsenic speciation and microbial community. 84.1% of As(III) was oxidized to As(V) in the acclimated sludge, decreasing the toxicity of As(III) to nitritation consortia. Insight to the microbial community, the relative abundances of Thermaceae and Phycisphaeraceae responsible for As(III) oxidation were increased to 7.4% and 6.6% under the stress of high-concentration As(III), respectively. Further, these increased arsenite-oxidizing bacteria probably accepted electron acceptor NO2- from ammonia-oxidizing bacteria to oxidize As(III). Our results indicated that microbial As(III) oxidation was the dominant detoxification pathway, providing new insights into nitritation characteristics under long-term As(III) stress.

Hydroxylamine addition enhances fast recovery of anammox activity suffering Cr(VI) inhibition.

Hydroxylamine (NH2OH), one of the most important intermediates of anammox was employed to test the recovery performance because of its stimulation to anammox bacteria. Batch test indicated simultaneous addition of 1.83 ~ 9.17 mg N /L NH2OH relieved Cr(VI) inhibition because of extracellular reduction to Cr(III). The recovery efficiency (RE) was over 166%, with the effluent Cr(VI) and Cr(III) below 0.25 and 0.12 mg/L, respectively. Anammox activity after Cr(VI) inhibition was effectively recovered by 8 mg N/L NH2OH with RE at 218%. The long-term operation showed 1 ~ 2 mg N/L NH2OH accelerated the recover speed of nitrogen removal rate with 2.84 folds, as well as improving NH4+ conversion ratio and reducing NO3- production. After 55 days recovery, extracellular polymeric substance concentration, anammox activity and heme content recovered better with NH2OH addition. This study will provide the theoretical basis for rapid recovery of anammox activity by NH2OH when suffering Cr(VI) inhibition.

Development and simulation of a struvite crystallization fluidized bed reactor with enhanced external recirculation for phosphorous and ammonium recovery.

Recovering nitrogen and phosphorus from waste water in the form of struvite is an effective way to recycle resources. The insufficient purity of the resulting struvite and the large loss of nitrogen and phosphorus are the challenges at present. Therefore, it is urgent to develop innovative method in struvite crystallization process for efficient nitrogen and phosphorus recovery. This study proposed a crystallization method to reduce the loss of nitrogen and phosphorus by a struvite fluidized bed reactor (FBR) with optimized structure and operation conditions. The properties of struvite obtained under various conditions in the reactor were studied, and the internal operating conditions of the reactor were simulated with COMSOL Multiphysics to verify the effectiveness of the reactor optimization. This reactor achieved stable operation under the conditions of N/P = 1:1 and pH = 9.0. The purity of struvite obtained reached 98.5%, the conversion rate of ammonia nitrogen reached 97.2%, and struvite crystals could grow to 84 µm within 24 h. The simulation results showed that the Venturi tubes installed at multiple locations increased the turbulent energy to 4 × 10-4 m2/s2, which greatly improved the mass transfer efficiency. The trajectory of the crystal particles was consistent with the fluid flow field, which promoted the purification and growth of the crystal. In general, the new FBR with enhanced external recirculation would be a very feasible way to improve crystal growth and crystal purification of struvite, and it could enhance the recovery efficiency of nitrogen and phosphorus with reduced cost.

Elucidating the effect of mixing technologies on dynamics of microbial communities and their correlations with granular sludge properties in a high-rate sulfidogenic anaerobic bioreactor for saline wastewater treatment.

In this study, three lab-scale anaerobic sulfidogenic bioreactors were operated independently using three different mixing modes (hydraulic, mechanical and pneumatic). One-way ANOVA test indicated various performance parameters (e.g. sulfate reduction and sulfide production) and granular sludge properties (e.g. EPS and particle size) statistically different in three mixing modes. Principal component analysis (PCA) and OTUs-based network demonstrated bacterial composition greatly varied among the three mixing modes. The phylum Proteobacteria was predominant among the bacterial communities, and the genus Desulfobacter (35.1% in hydraulic, 31.1% in mechanical and 27.4% in pneumatic sample) was the most dominant SRB. The PCA/Pearson's correlation analysis confirmed SRB had significant positive relationship with sludge properties (e.g. particle size). PICRUSt data highlighted that bacterial communities contained diverse predicted functions including sulfur metabolism enzymes (sulfite reductase and adenylylsulfate reductase). The findings of this research could be helpful for selection of an appropriate mixing technology for anaerobic sulfidogenic or similar bioprocess.

Long-term domestication to Mn stresses alleviates the inhibition on anammox process.

Heavy metals such as Mn2+ are common contaminants in ammonium-rich wastewater. The information of Mn2+ effect on anammox process needs further investigation. The short- and long-term effects of Mn2+ on anammox were explored by anammox granular sludge. Batch tests showed that the half inhibition value (IC50 ) of Mn2+ was 4.83 mg/L. The anammox activity was severely inhibited in 0.5 hr under 15 mg/L Mn2+ . However, after long-term domestication by increasing the concentration of Mn2+ , both the low-load reactor (R1) and the high-load reactor (R2) performed well, achieving volumetric nitrogen removal rate of 6.36 kg/(m3 ·d) and 13.99 kg/(m3 ·d), respectively. The average ammonium and nitrite removal efficiency of both reactors under 200 mg/L Mn still maintained above 90%. The results from long-term reactors' operation showed that the serious inhibition effect indicated by the batch test was significantly exaggerated. The granules became dispersed after long-term operation in the high-load reactor (R2) which might be correlated to the high osmotic pressure caused by high Mn2+ load, and the mechanism needs to be investigated further. PRACTITIONER POINTS: The half inhibition value of Mn2+ on anammox sludge was 4.83 mg/L in batch experiment. 200 mg/L Mn2+ did not cause any inhibition on anammox process during long-term operation. Granular sludge is finer under high nitrogen loads with 200 mg/L Mn stress.

Synthesis of core-shell UiO-66-poly(m-phenylenediamine) composites for removal of hexavalent chromium.

The present research developed a direct in situ heterogeneous method to synthesize UiO-66-poly(m-phenylenediamine) core-shell nanostructures by inducing assembly of m-phenylenediamine radical on UiO-66 surfaces. The strong interaction between negative charged UiO-66 and positive radical from the oxidation of monomer is the major driving force. The produced UiO-66-poly(m-phenylenediamine) composites exhibited a distinct core-shell morphology with controllable surface features. The UiO-661-PmPD0.5 showed a uniform PmPD shell with a thickness of 40-60 nm and the nanocomposite exhibited a high specific surface area of 319.77 m2 g-1. Moreover, the Cr(VI) adsorption amount of the polymeric shell in the nanocomposites can reach as high as 745 mg g-1, far beyond the performance of the original PmPD. The adsorption tends to be equilibrium within 300 min. This research opens a hopeful window for facile and large-scale fabrication of core-shell nanostructures with controllable core-shell configuration, exhibiting high prospect in heavy metal removal from water.