Comparison of two carbonaceous supported Fe-rich adsorbents for arsenate removal: A functionalisation and mechanistic study with applicability to groundwater treatment.

The presence of arsenic in groundwater, and through this in drinking water, has been shown to present a serious risk to public health in many regions of the world. In this study, two iron-rich carbonous adsorbents were compared for the removal of arsenate (As(V)) from groundwater. Biochars (FeO-biochar and FeO-pyrochar) derived from biomass waste were functionalised in two different ways with iron chloride for comparation. Batch and dynamic parameters were optimised to achieve >99% As(V) removal efficiency. Experimental data were best described by the pseudo-second order kinetic model, while multi-stage diffusion appeared to limit mass transfer of As(V). Among the isotherm models evaluated, the Freundlich model best described the experimental results with high correlation coefficients (R2 ≥ 0.94) for both adsorbents. Monolayer adsorption capacities were found to be 4.34 mg/g and 8.66 mg/g for FeO-biochar and FeO-pyrochar, respectively. Batch studies followed by instrumental characterisation of the materials indicated the removal mechanisms involved to be electrostatic interactions (outer-sphere), OH- ligand exchange (inner-sphere complexation) and hydrogen bonding with functional groups. Higher pHpzc (9.1), SBET (167.2 m2/g), and iron/elemental content for the FeO-pyrochar (compared with the FeO-biochar) suggested that both surface chemistry and porosity/surface area were important in adsorption. Dynamic studies showed FeO-pyrochar can be used to remove As(V) from groundwater even at low 'environmental' concentrations relevant to legislative limits (<10 µg/L), whereby 7 g of FeO-pyrochar was able to treat 5.4 L groundwater.

Pilot-scale phosphate recovery from wastewater to create a fertiliser product: An integrated assessment of adsorbent performance and quality.

Eutrophication and the predicted limited future availability of rock phosphate has triggered the increased development of phosphorus (P) recovery technologies, however, for remote regions, recovery solutions are still limited. Here, we report on a novel pilot-scale technology (FILTRAFLOTM-P reactor) to recover phosphate (PO43-) from wastewater effluent through a filtration/adsorption process in a rural setting. This unit employs enhanced gravitational filtration through adsorption media (here, a novel KOH deacetylated crab carapace based chitosan-calcite material (CCM)) with continuous self-backwashing. Trials were designed to assess how the FILTRAFLOTM-P unit would operate under 'real' conditions (both at low and high PO43- levels), and to ascertain the effectiveness of the adsorbent to recover phosphate from final effluent. High removal was achieved at low phosphate concentrations, bringing the residual effluent PO43- level below 1 mg/L (EU limit for sensitive water bodies), while phosphate was efficiently harvested (at more than 50%) at higher PO43- levels. Surface microprecipitation and inner-sphere complexation were postulated as the main PO43- adsorption mechanisms through XRD, XPS and EDX elemental mapping. Further, a quality assessment of the P-enriched CCM (which could be used as a potential soil amendment) was undertaken to consider elemental composition, microbiological assessment and quantification of organic micropollutants. Quality analysis indicated ∼2.5% P2O5 present, trace levels (well below legislative limits) of heavy metals and extremely low levels of organic pollutants (e.g., PCBs, pharmaceuticals). No detectable levels of target bacterial pathogens were observed. Pot trials showed that ryegrass cultivated with the addition of the CCM adsorbent achieved higher plant dry matter and P concentration when compared to unfertilised controls, with a slow-release kinetic pattern. This study showed that CCM used with the FILTRAFLOTM-P pilot reactor has high potential to recover phosphate from effluents and encourage resource recovery via bio-based management of waste.

Enhanced phosphate removal and potential recovery from wastewater by thermo-chemically calcinated shell adsorbents.

Shell from the seafood processing industry is an under-utilised waste resource worldwide. Calcite, the major component of shell is commonly used in wastewater treatment for the removal of phosphorus (P). Here, mussel and oyster shell-based adsorbents (MSB and OSB) were used for removal of P as phosphate (PO43-) from aqueous solution and secondary wastewater, following preparation through chemical calcination at 700 °C. Batch adsorption experiments were carried out to identify the effects of various operating parameters (e.g., pH, dosage, contact time, initial concentration of P ions, co-existing ions), while a desorption study helped to understand the availability of the bonded P. The optimal contact time for PO43- removal was 120 min using both adsorbents with the dose at 200 mg. Characterisation of the adsorbent was performed using SEM-EDX, pHpzc, BET, FTIR and XRD. The XRD analysis showed that both calcite and lime were present on the surface of the shell particles. P was adsorbed effectively through inner-sphere complexation and surface microprecipitation mechanisms, while an enhanced maximum P adsorption capacity of 12.44 mg/g for MSB and 8.25 mg/g for OSB was reached. The Redlich-Peterson isotherm model fitted well with the equilibrium isotherm data (R2 ≥ 0.97) which also suggested a heterogenic surface. The desorption study (on the saturated adsorbent) found that ~97% of bonded P could be plant available in soil. These results suggest that a shell-based adsorbent can serve as a promising material for P removal from real wastewater effluent and subsequently could be used as a soil conditioner.

A SPE-HPLC-MS/MS method for the simultaneous determination of prioritised pharmaceuticals and EDCs with high environmental risk potential in freshwater.

This work describes the development, optimisation and validation of an analytical method for the rapid determination of 17 priority pharmaceutical compounds and endocrine disrupting chemicals (EDCs). Rather than studying compounds from the same therapeutic class, the analyses aimed to determine target compounds with the highest risk potential (with particular regard to Scotland), providing a tool for further monitoring in different water matrices. Prioritisation was based on a systematic environmental risk assessment approach, using consumption data; wastewater treatment removal efficiency; environmental occurrence; toxicological effects; and pre-existing regulatory indicators. This process highlighted 17 compounds across various therapeutic classes, which were then quantified, at environmentally relevant concentrations, by a single analytical methodology. Analytical determination was achieved using a single-step solid phase extraction (SPE) procedure followed by high-performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS). The fully optimised method performed well for the majority of target compounds, with recoveries >71% for 15 of 17 analytes. The limits of quantification for most target analytes (14 of 17) ranged from 0.07 ng/L to 1.88 ng/L in river waters. The utility of this method was then demonstrated using real water samples associated with a rural hospital/setting. Eight compounds were targeted and detected, with the highest levels found for the analgesic, paracetamol (at up to 105,910 ng/L in the hospital discharge). This method offers a robust tool to monitor high priority pharmaceutical and EDC levels in various aqueous sample matrices.

Reply to comments on "Low-cost chitosan-calcite adsorbent development for potential phosphate removal and recovery from wastewater effluent" by Pap et al. [Water research 173 (2020) 115573].

This letter is in response to the comments of Dr Hu and Dr Zhang on "Low-cost chitosan-calcite adsorbent development for potential phosphate removal and recovery from wastewater effluent" (Pap et al., 2020). We thank Dr Hu and Dr Zhang for their interest and comments, and having reflected, we wish to provide some clarification.

Low-cost chitosan-calcite adsorbent development for potential phosphate removal and recovery from wastewater effluent.

Phosphorous (P) recovery from wastewater will become increasingly vital in the future as terrestrial rock phosphate deposits are expended. Effective management of P as a critical resource will require new techniques to recover P from wastewater, ideally in a form that can be used in agriculture as fertiliser. In this study, batch and fixed-bed column conditions were tested using a novel KOH deacetylated calcite-chitosan based adsorbent (CCM) for P removal from aqueous solutions and wastewater effluents. The unique characteristics of this adsorbent as a phosphate adsorbent were the result of rich surface functionality (amine and sulphur functional groups of the chitosan and proteins) and the CaCO3 content (providing donor ligands; and additionally beneficial if the material were used as fertiliser, buffering soil acidification caused by nitrogen application). The maximum P adsorption capacity was determined to be 21.36 mgP/g (at 22 °C) and the endodermic process reached equilibrium after 120 min. The experimental data was best described using a Langmuir isotherm and a pseudo-second order kinetic model. The diffusion kinetic analysis highlighted the importance of both film and intraparticle mass-transport. Material characterisation suggested that the adsorption process involved interactions between P and functional groups (mostly -NH3+) due to electrostatic interaction on the chitosan chain or involved ligand exchange with CO32-. Analysis of materials using X-Ray Powder Diffraction (XRPD) and Thermogravimetric Analysis (TGA) indicated a microprecipitation-type mechanism may occur through the formation of hydroxylapatite (Ca5(PO4)3(OH)). Desorption studies demonstrated that the P-laden CCM (derived from crab carapace) had the potential to be reused in soil amendment as a slow-release P fertiliser. The effects of different operating parameters were explored in a fixed-bed column, and the experimental data fitted well to the Clark model (R2 = 0.99). The CCM also showed excellent P adsorption potential from secondary and final wastewater effluent in dynamic conditions, even at low P concentrations. Finally, a scale-up approach with cost analysis was used to evaluate the price and parameters needed for a potential large-scale P recovery system using this adsorbent.

Synthesis optimisation and characterisation of chitosan-calcite adsorbent from fishery-food waste for phosphorus removal.

Here, Box-Behnken design (BBD) approaches were utilised to optimise synthesis methodology for the chitosan-calcite rich adsorbent (CCM) made from fishery-food waste material (crab carapace), using low-temperature activation and potassium hydroxide (KOH). The effect of activation temperature, activation time and impregnation ratio was studied. The final adsorbent material was evaluated for its phosphorus (P) removal efficiency from liquid phase. Results showed that impregnation ratio was the most significant individual factor as this acted to increase surface deacetylation of the chitin (to chitosan) and increased the number of amine groups (-NH2) in the chitosan chain. P removal efficiency approached 75.89% (at initial P concentration of 20 mg/L) under optimised experimental conditions, i.e. where the impregnation ratio for KOH:carapace (g/g) was 1:1, the activation temperature was 105 °C and the activation time was 150 min. Predicted responses were in good agreement with the experimental data. Additionally, the pristine and CCM material were further analysed using scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX), Brunauer-Emmett-Teller technique (BET), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermal gravimetric analysis (TGA). Characterisation showed enhancements in surface chemistry (introducing positively charged amine groups), textural properties and thermal stability of the CCM.

A review of the potential utilisation of plastic waste as adsorbent for removal of hazardous priority contaminants from aqueous environments.

There is growing global awareness of the presence and negative impacts of waste plastic in the marine environment. Risks to wildlife include ingestion and entanglement for macro-plastic (larger than 5 mm in length), alongside food chain transfer for micro-plastics (less than 5 mm in length). Plastics in the marine environment have also been shown to adsorb and accumulate contaminants from seawater, e.g., heavy metals and hydrophobic organic compounds. This means that plastics can additionally act as vectors for transport of contaminants, permitting ecotoxicological risks to be spatially extended. However, the ability of waste plastic to adsorb pollutants also offers potential opportunity, if they can be used for the decontamination of wastewater. Here, we provide an overview of marine plastic types and distribution, and then systematically assess their potential to be repurposed as novel adsorbents. Data published in recent years are interrogated to gain an overview of the interaction mechanisms between marine plastics and both organic and inorganic contaminants. In addition, factors that may be exploited to enhance their performance in removal of contaminants are also reviewed and prioritised, e.g., surface modification and activation. This paper highlights the novel potential of repurposing plastic waste for wastewater treatment applications and seeks to identify key knowledge gaps and future research priorities for scientists and engineers.

Comparison of sustainable biosorbents and ion-exchange resins to remove Sr2+ from simulant nuclear wastewater: Batch, dynamic and mechanism studies.

Removal of Sr2+ from aqueous media presents particular challenges, especially in complex wastes such as nuclear industry liquors. Commercial sorbents while effective, can be highly expensive and subject to negative effects from competing ions. Here we evaluate two potential biosorbents (crab carapace and spent distillery grain) as potential alternatives and compare their performance to two commercial sorbents for Sr2+ removal at industrially relevant concentrations (low mg/L). Physical and structural characterization of the materials was undertaken, and batch and dynamic studies were performed on Sr2+ solutions and simulated nuclear wastewater. Sorption performance was quantified with respect to contact time, initial concentration and ion-competition. Removal efficiencies were 20-70% for the biosorbents compared to 55-95% for the commercial materials. Results indicated sorption was predominantly through monolayer coverage on homogenous sites and could be described using a pseudo-second-order kinetic model. Studies with the simulant liquor showed Sr2+ sorption was reduced by 10-40% due to ion-competition for sites. Characterization of biosorbents before and after Sr2+ sorption suggested that outer-sphere complexation and ion-exchange were the primary Sr2+ removal mechanisms. The efficiency of crab carapace for Sr2+ removal from aqueous media (with adsorption capacity 3.92 mg/g.) at industrially relevant concentrations, together with its mechanical stability, implementation and disposal cost, makes it a competitive option compared to other biosorbents and commercial materials reported in the literature.

Geochemical landscapes as drivers of trace and toxic element profiles in wild red deer (Cervus elaphus).

Tissue concentrations of essential trace and toxic elements in red deer (Cervus elaphus) are associated with the plants, soil and water they ingest. As such, variation in tissue concentrations is associated with variation in local geochemistry and bioavailability of elements. Physiological factors such as liver fluke (Fasciola hepatica) infection, breeding status, and in-tissue element interactions may also affect tissue concentrations, though their effects in red deer are not well understood. The primary objective of this study was therefore to survey wild red deer liver element concentrations across a range of geographically distinct populations during the Scottish red deer stalking season; and, in so doing, establishes element reference ranges while also exploring geographic and temporal variation and physiological factors. Livers were sampled from carcasses intended for human consumption on nine hunting estates during two seasons (2012-13, 2013-14). Samples were digested and analysed by ICP-OES for essential trace elements (Co, Cu, Fe, Mn, Mo, Se, Zn) and for Cd. Data (n=787) were modelled against cull location, date, and F. hepatica diagnosis. Interactions between elements within liver, and differences in element profiles between estates, were explored by principal component analysis. Our results revealed marked geographic variation in Cd, Cu and Se, where up to four-fold differences in median element concentrations occurred between estates, and, in males, Mn, Mo and Zn declined as the breeding season approached. In both sexes, within-liver associations (Cd-Cu-Se and Mn-Mo-Zn) were found. In females, liver Zn was greater on average in individuals that were not infected with F. hepatica. This study is the first to quantify geographic variation in Scottish red deer liver element concentrations; the drivers of which remain to be explored (and may be management related), and, the consequence of which may affect sub-clinical health.

Prevalence of Liver Fluke (Fasciola hepatica) in Wild Red Deer (Cervus elaphus): Coproantigen ELISA Is a Practicable Alternative to Faecal Egg Counting for Surveillance in Remote Populations.

Red deer (Cervus elaphus) are hosts of liver fluke (Fasciola hepatica); yet, prevalence is rarely quantified in wild populations. Testing fresh samples from remote regions by faecal examination (FE) can be logistically challenging; hence, we appraise frozen storage and the use of a coproantigen ELISA (cELISA) for F. hepatica surveillance. We also present cELISA surveillance data for red deer from the Highlands of Scotland. Diagnoses in faecal samples (207 frozen, 146 fresh) were compared using a cELISA and by FE. For each storage method (frozen or fresh), agreement between the two diagnostics was estimated at individual and population levels, where population prevalence was stratified into cohorts (e.g., by sampling location). To approximate sensitivity and specificity, 65 post-slaughter whole liver examinations were used as a reference. At the individual level, FE and cELISA diagnoses agreed moderately (κfrozen = 0.46; κfresh = 0.51), a likely reflection of their underlying principles. At the population level, FE and cELISA cohort prevalence correlated strongly (Pearson's R = 0.89, p < 0.0001), reflecting good agreement on relative differences between cohort prevalence. In frozen samples, prevalence by cELISA exceeded FE overall (42.8% vs. 25.8%) and in 9/12 cohorts, alluding to differences in sensitivity; though, in fresh samples, no significant difference was found. In 959 deer tested by cELISA across the Scottish Highlands, infection prevalence ranged from 9.6% to 53% by sampling location. We highlight two key advantages of cELISA over FE: i) the ability to store samples long term (frozen) without apparent loss in diagnostic power; and ii) reduced labour and the ability to process large batches. Further evaluation of cELISA sensitivity in red deer, where a range of fluke burdens can be obtained, is desirable. In the interim, the cELISA is a practicable diagnostic for F. hepatica surveillance in red deer, and its application here has revealed considerable geographic, temporal, sex and age related differences in F. hepatica prevalence in wild Scottish Highland red deer.

Source apportionment and risk assessment of emerging contaminants: an approach of pharmaco-signature in water systems.

This paper presents a methodology based on multivariate data analysis for characterizing potential source contributions of emerging contaminants (ECs) detected in 26 river water samples across multi-scape regions during dry and wet seasons. Based on this methodology, we unveil an approach toward potential source contributions of ECs, a concept we refer to as the "Pharmaco-signature." Exploratory analysis of data points has been carried out by unsupervised pattern recognition (hierarchical cluster analysis, HCA) and receptor model (principal component analysis-multiple linear regression, PCA-MLR) in an attempt to demonstrate significant source contributions of ECs in different land-use zone. Robust cluster solutions grouped the database according to different EC profiles. PCA-MLR identified that 58.9% of the mean summed ECs were contributed by domestic impact, 9.7% by antibiotics application, and 31.4% by drug abuse. Diclofenac, ibuprofen, codeine, ampicillin, tetracycline, and erythromycin-H2O have significant pollution risk quotients (RQ>1), indicating potentially high risk to aquatic organisms in Taiwan.

Introduction of human pharmaceuticals from wastewater treatment plants into the aquatic environment: a rural perspective.

Incomplete removal of pharmaceuticals during wastewater treatment can result in their discharge into the aquatic environment. The discharge of pharmaceuticals in wastewater treatment plant (WWTP) effluents into rivers, lakes and the oceans has led to detectable concentrations of pharmaceuticals in the aquatic environment in many countries. However, to date studies of WWTP discharges into the aquatic environment have largely been confined to areas of relatively high population density, industrial activity or systems impacted on by such areas. In this work, two sites in the far north of Scotland were used to assess whether, and which, pharmaceuticals were being introduced into natural waters in a rural environment with low population density. Samples from two WWTPs (with differing modes of operation), and one receiving water, the River Thurso, were analysed for the presence of 12 pharmaceuticals (diclofenac, clofibric acid, erythromycin, ibuprofen, mefenamic acid, paracetamol, propranolol, sulfamethoxazole, tamoxifen, trimethoprim and dextropropoxyphene). Ten of the 12 pharmaceuticals investigated were detected in at least one of the 40 WWTP effluent samples. Maximum concentrations ranged from 7 ng L(-1) (sulfamethoxazole) to 22.8 µg L(-1) (paracetamol) with diclofenac and mefenamic acid being present in all of samples analysed at concentrations between 24.2 and 927 ng L(-1) and 11.5 and 22.8 µg L(-1), respectively. Additionally, the presence of four pharmaceuticals at ng L(-1) levels in the River Thurso, into which one of the WWTPs discharges, shows that such discharges result in measurable levels of pharmaceuticals in the environment. This provides direct evidence that, even in rural areas with low population densities, effluents from WWTPs can produce quantifiable levels of human pharmaceutical in the natural aquatic environment. These observations indicate that human pharmaceuticals may be considered as contaminants, with potential to influence water quality, management and conservation not only in urban and industrial regions but also those more rural in nature.

Heat-stress and light-stress induce different cellular pathologies in the symbiotic dinoflagellate during coral bleaching.

Coral bleaching is a significant contributor to the worldwide degradation of coral reefs and is indicative of the termination of symbiosis between the coral host and its symbiotic algae (dinoflagellate; Symbiodinium sp. complex), usually by expulsion or xenophagy (symbiophagy) of its dinoflagellates. Herein, we provide evidence that during the earliest stages of environmentally induced bleaching, heat stress and light stress generate distinctly different pathomorphological changes in the chloroplasts, while a combined heat- and light-stress exposure induces both pathomorphologies; suggesting that these stressors act on the dinoflagellate by different mechanisms. Within the first 48 hours of a heat stress (32°C) under low-light conditions, heat stress induced decomposition of thylakoid structures before observation of extensive oxidative damage; thus it is the disorganization of the thylakoids that creates the conditions allowing photo-oxidative-stress. Conversely, during the first 48 hours of a light stress (2007 µmoles m(-2) s(-1) PAR) at 25°C, condensation or fusion of multiple thylakoid lamellae occurred coincidently with levels of oxidative damage products, implying that photo-oxidative stress causes the structural membrane damage within the chloroplasts. Exposure to combined heat- and light-stresses induced both pathomorphologies, confirming that these stressors acted on the dinoflagellate via different mechanisms. Within 72 hours of exposure to heat and/or light stresses, homeostatic processes (e.g., heat-shock protein and anti-oxidant enzyme response) were evident in the remaining intact dinoflagellates, regardless of the initiating stressor. Understanding the sequence of events during bleaching when triggered by different environmental stressors is important for predicting both severity and consequences of coral bleaching.

Biosorption of Hg from aqueous solutions by crab carapace.

Carapace from the edible crab was assessed for the biosorption of Hg from aqueous solutions. Batch adsorption studies were used to determine the effects of contact time, pH, concentration, particle size and Cu(II) as a co-ion. The removal of Hg was fast and efficient, attaining >80.0% from 500 mg/L by 60 min. Specific uptake increased from 0.1 to 13.0mg/g as initial concentration increased from 0.5 to 1000 mg/L while the removal efficiency decreased from 100.0% over the 0.5-10.0mg/L range to 65.0% at 1000 mg/L. As particle size decreases from >2.5 to <0.15 mm, the Hg uptake increased from 1.4 to 8.3mg/g. In binary metal solutions, Cu(II) reduced the Hg removal by 80.0% while the presence of Hg increased Cu(II) removal by approximately 7.0%. Crab carapace is a readily available alkaline waste and easily processed into durable granular forms. Therefore, it offers potential as a low-cost alternative to commercial adsorbents or as a complimentary polishing process for the removal of Hg from acidic solutions.

Copper removal from wastewater using spent-grain as biosorbent.

The removal of Cu(II) ions from aqueous solutions using spent-grain was studied. The experimental data fitted the Langmuir isotherm and the maximum adsorption capacity of spent-grain was determined to be 10.47 mg g(-1) dry weight (pH 4.2). Kinetic studies showed the adsorption process followed pseudo second-order rate model. Column studies with synthetic Cu(II) solutions were used to investigate the effects of Cu(II) ion concentration, initial pH, flow rate and the presence of EDTA on the Cu(II) removal performance. When treating the spent-lees, the wastewater from the whisky distilling industry, the reduction of Cu(II) uptake capacity to 77.7% (solution pH adjusted to 4.5 with 1N NaOH) and 31.6% (pH 3.8 without adjustment) was observed compared to Cu(II) uptake capacity when treating synthetic Cu(II) solution. On the basis of the results and that spent-grain is an abundant and by-product from the whisky distilling industry we suggest that it can be economically and effectively applied as a biosorbent for the removal of Cu(II) ions from distilling wastewaters.

Quantification of human pharmaceuticals in water samples by high performance liquid chromatography-tandem mass spectrometry.

An improved analytical method for determination of human pharmaceuticals in natural and wastewaters with ng L(-1) sensitivity is presented. The method is applicable to pharmaceuticals from a wide range of therapeutic classes including antibiotics, analgesics, anti-inflammatories and anti-cancer compounds. Pharmaceuticals were extracted from waters using solid-phase extraction, and after concentration, analysed by high performance liquid chromatography with tandem mass spectrometric detection (HPLC-MS/MS). Identification of each compound was secured using retention time and by the selected reaction monitoring of two transitions, one of which was additionally used for quantification. Limits of detection ranged from 0.03 to 0.96 ng L(-1) and were up to two orders of magnitude lower than those of previously published methods. The method was validated using spiked samples prepared from tap, river and sea water as well as wastewater effluents, collected from the North of Scotland. Analysis of wastewater effluents revealed the presence of mefenamic acid, ibuprofen, erythromycin, diclofenac and trimethoprim. None of the selected pharmaceuticals were detected in river, tap or sea water samples.

Effective removal of zinc ions from aqueous solutions using crab carapace biosorbent.

The carapace of the crab (Cancer pagurus), a waste material disposed of by the seafood industry, has recently been shown to have potential as a biosorbent for the removal of metals from aqueous media. Crab carapace in the particle size ranges 0.25-0.8mm and 0.8-1.5mm were used to investigate the effects of agitation speed, contact time, metal concentration and initial pH on the removal of Zn(2+). In sequential-batch process Zn(2+) uptakes of 105.6 and 67.6 mg/g were recorded for 0.25-0.8 mm and 0.8-1.5 mm particles, respectively, while values of 141.3 and 76.9 mg/g were recorded in fixed-bed column studies. Binary-metal studies showed that the presence of Cu(2+) or Pb(2+) significantly suppressed Zn(2+) uptake. This study confirms that crab carapace may be considered a viable and cost-effective alternative to commercial activated carbon or ion-exchange resins for the removal of metals from aqueous media.