Reuse of Drinking Water Treatment Waste for Remediation of Heavy Metal Contaminated Groundwater

Lime softening produces an estimated 10,000 metric tons of dry drinking water treatment wastes (DWTW) per year, costing an estimated one billion dollars annually for disposal worldwide. Lime softening wastes have been investigated for reuse as internal curing agents or supplementary cementitious materials in concrete as well as a high-capacity sorbent for heavy metal removal. Lead, cadmium, and zinc are common heavy metals in groundwater contaminated by mine tailings. Cement-based filter media (CBFM) are a novel material-class for heavy metal remediation in groundwater. This study investigated the incorporation of DWTW as a recycled, low-cost additive to CBFM for the removal of lead, cadmium, and zinc. Jar testing at three different metal concentrations and breakthrough column testing using synthetic groundwater were performed to measure removal capacity and reaction kinetics. Jar testing results show as DWTW content increases at low concentrations, removal approaches 100% but at high metal concentrations removal decreases due to saturation or exhaustion of the removal mechanisms. Removal occurs through the formation of metal carbonate precipitates, surface sorption, and ion exchange with calcium according to the preferential series Pb⁺² > Zn⁺² > Cd²⁺. Removal kinetics were also measured through column testing and exceeded estimated calculations derived from batch jar testing isotherms due to the large formation of oolitic metal carbonates. Lead, cadmium, and zinc was concentrated in the column precipitates from 0.29, 0.23, and 20.0 μg/g in the influent solution to approximately 200, 130, 14,000 μg/g in the reacted DWTW-CBFM. The control and DWTW-CBFM columns had statically similar removal for zinc and lead. In the DWTW-CBFM, cadmium had decreased removal of approximately 25% due to proportionately decreased hydroxide content from cement replacement with 25% DWTW. This study shows the potential for DWTW as an enhancement to CBFM, thereby valorizing an otherwise waste material. Furthermore, the concentrative abilities of CBFM through precipitate and oolitic mineral formation could provide a minable waste product and close the waste-product cycle for DWTW.     

Flame Atomic Absorption Spectrometry Determination of Trace Amounts of Cadmium and Zinc in Water Samples after Preconcentration onto Modified Amberlite XAD‐4 Resin

In the present article, a procedure for the simultaneous separation and preconcentration of trace amounts of cadmium and zinc is proposed. It is based on the adsorption of cadmium and zinc ions onto a column of Amberlite XAD‐4 resin loaded with aluminon reagent. Cadmium and zinc ions are quantitatively retained on the column in the pH range from 6.5–7.5, at a flow rate of 2 mL min^–1. The cadmium and zinc ions are eluted with 5.0 mL of 5 mol L^–1 HNO₃ solution. Cadmium and zinc are measured by flame atomic absorption spectrometry (FAAS). In the present case, 0.1 μg of cadmium and 0.5 μg of zinc can be concentrated in the column from 1000 mL of aqueous sample, where their concentrations are as low as 0.1 and 0.5 ng mL^–1, respectively. The relative standard deviations, for seven replicated determinations of 1.0 μg mL^–1 of cadmium and zinc, are 1.2 and 1.1%, respectively. The detection limits for cadmium and zinc in the original solution are 0.02 and 0.11 ng mL^–1, respectively. The interference of a large number of anions and cations has been studied and the optimized conditions are utilized for the determination of trace amounts of cadmium and zinc in different environmental and standard samples.     

The uptake of dissolved zinc and cadmium by the decapod crustacean Palaemon elegans

The rates of uptake of the heavy metals zinc and cadmium from solution were measured in the caridean decapod crustacean Palaemon elegans. When radioactively-labelled zinc and cadmium were present together with both at dissolved concentrations of 20 μg l⁻¹, the rate of zinc uptake by the decapod decreased and the rate of cadmium uptake increased in comparison with the uptake rates of each metal in single metal exposures of 20 μg l⁻¹. This effect can be interpreted as a result of competition between the two metals for uptake routes. The rate of zinc uptake by individual P. elegans is positively linearly correlated with the rate of cadmium uptake. Thus, some individuals have inherently higher metal uptake rates than others, although such uptake rates are also greatly affected by the stage in the moult cycle.     

Age-related change and distribution of cadmium and zinc concentrations in the Steller sea lion (Eumetopias jubata) from the coast of Hokkaido,Japan

Tissue cadmium and zinc levels in Steller sea lions have been analysed to elucidate the body distribution of these metals and their age-related accumulation. A significant correlation between age (0.7–8.8 year old) and renal and hepatic cadmium concentration was noted. Of the tissues examined, the kidney manifested the highest cadmium content (mean: 20.9 μg g^?1 dry wt). A similar zinc distribution pattern was observed; its concentration was more uniform among tissues than that of cadmium. The tissue cadmium concentration in the Steller sea lion was lower than in other pinnipeds from various areas, possibly due to their feeding habits which may represent a major pathway of metal accumulation.     

Stable isotopes and metal contamination in caged marine mussel Mytilus galloprovincialis

Metal concentrations and isotopic composition were measured in different tissues of the mussel Mytilus galloprovincialis in waters of the Balearic Islands (Western Mediterranean) in order to assess pollution levels. The isotopic composition was correlated with lead, cadmium, selenium and nickel obtained from the digestive gland and foot of the mussels. Significant negative correlations were found between cadmium, selenium and zinc and the mussel foot, mainly for ¹³C. Significant correlations were also found between lead and cadmium and the digestive gland. Pearson correlations indicated that the ¹³C isotopic signal in foot is a good proxy for the concentration of metals such as lead, cadmium, selenium and zinc. Similarly, ¹⁵N isotopic signatures in the digestive gland reflected the lead and cadmium concentration.     

Auswirkung von Schwermetallgemischen auf die biologische Behandlung naphthalinsulfonsäurehaltiger Abwässer

Effect of Mixtures of Heavy Metals on the Biological Treatment of Sewages Containing Naphthalenesulfonic Acid Biological wastewater treatment processes can be destabilized considerably by heavy metals. In this investigation, the effect of loadings of heavy metals on the degradation of naphthalene-2-sulfonic acid (2NS) by immobilized bacteria in continuously operated airlift-loop reactors was studied. Shock loadings with mixtures of cadmium and nickel, or cadmium and zinc, respectively, resulted in increases in inhibition compared to those observed with the single metals. In contrast, the 2NS-degradation was less inhibited by shock loadings with mixtures of nickel and zinc than by the single metal ions. Repeated shock loadings up to 100 mg L^?1 nickel and 1000 mg L^?1 zinc effected an adaptation of the microorganisms. Continuous loadings with up to 10 mg L^?1 cadmium and nickel each, or with 50 mg L^?1 nickel and 210 mg L^?1 zinc, respectively, did not inhibit the degradation of 2NS. The permanent loadings led to an adaptation of the bacteria with an increased biosynthesis of proteins from 0.2 to 0.5 g g^?1 cell dry weight. However, if the immobilized cells were incubated with mixtures of cadmium and nickel, the specific polysaccharide content decreased to less than 0.2 g g^?1 cell dry weight, resulting in a detachment of the biofilms.     

Trace metal content in the American oyster

Information about the transfer of pollutants from adult aquatic animals to their progeny is relatively unknown. The present study was designed to measure the transfer of metals from adults to eggs of the American oyster. Two groups of oysters containing significantly different levels of copper and cadmium were induced to spawn, the eggs were collected and trace metal contents measured. The eggs from both groups of oysters contained the same amount of copper, while cadmium levels were below detectable limits in both groups of eggs. Silver, lead, and zinc concentrations also were determined. The concentrations of these metals were similar for both groups of adults and eggs; thus, no conclusion could be made about the transfer of these three metals from adults to eggs of oysters.     

Transformation of Tobacco with ScMTII Gene‐Enhanced Cadmium and Zinc Accumulation

Genetic transformation is gaining importance for developing plant types suitable to metal accumulate and/or hyperaccumulate. In this study, the transgenic tobacco plant which transferred the ScMTII gene from Saccharomyces cerevisiae to wild type tobacco cultivar Petite Havana (SR1) was grown on soils with low and high cadmium (Cd) and zinc (Zn) concentrations in a growth chamber for 6 weeks and compared to wild type tobacco for Cd and Zn accumulation. Cadmium and Zn accumulations in the transgenic and wild type tobacco plants were increased with the increasing Cd and Zn concentrations. Unlike Zn, the transgenic plant accumulated significantly higher amount of Cd compared to the wild type control plants. Shoot Cd concentrations of transgenic tobacco in higher Cd dosages reached the above the hyperaccumulation threshold value of 100 mg Cd kg^?1 in the dry weight (DW). Transgenic tobacco accumulated 354, 400, 372, and 457 mg Cd kg^?1 DW, for 10, 20, 40, and 80 mg Cd kg^?1 soil treatments, respectively. These values are 3.5–4.5‐fold higher than that of Cd hyperaccumulation threshold value. With 10 mg kg^?1 Cd treatment, the bioconcentration factor (BCF) of transgenic tobacco plants for Cd reached up to 35 in which the threshold value for BCF should be at least 10. Our results showed that the transgenic tobacco may be used as a good Cd hyperaccumulator plant and for phytoextraction of Cd contaminated soils, but not for Zn.     

Metal Concentrations in Tissues of Rabbitfish (Siganus oramin) Collected from Tolo Harbour and Victoria Harbour in Hong Kong

Rabbitfish (Siganus oramin, also known as Siganus canaliculatus) samples were collected from different coastal sites in the Victoria Harbour and Tolo Harbour in the summer of 1997 for the analyses of metal (cadmium, copper, lead, and zinc) concentrations in liver, gills, and muscle. The overall metal concentrations in rabbitfish tissues were below regulatory levels implemented through the government of Hong Kong. For cadmium and lead, the metal concentrations detected were place concentrations here. Generally speaking, the metal concentrations in liver samples were higher than that of gills and muscle. However, the mean values of lead concentrations of rabbitfish from the Tolo Harbour and Victoria Harbour are higher in the gills than in the livers.     

Distribution of trace metals in the Odra River system: Water–suspended matter–sediments

Extensive investigations of trace metals concentrations in water, suspended particulate matter (SPM) and bottom sediments of the whole Odra River system were carried out over the years 1997–2000. The vertical distribution of selected metals and their mobility were also studied in the sediment cores from upper and middle river sections. Significant levels of metal contamination were found. Median concentrations (Cd, Pb, Cu, Zn and As) in the SPM and sediments were (mg kg⁻¹) 7.1 and 8.9 Cd, 128 and 146 Pb, 81 and 119 Cu, 1198 and 1204 Zn, 48 and 54 As, respectively. The highest metal pollution of the Odra River solids was found with cadmium, zinc, lead and arsenic, showing high similarity in their frequency distributions in both SPM and sediments. Cd, Zn and As appear to be of particular concern because of the high levels, that appear to be bioavailable, and their high mobility. The exchangeable and carbonate chemical forms of Cd and Zn reached up to 50% of their total amount. Besides the determination of total metal concentration, the metal chemical forms in river solids were investigated. The results of very wide studies of the Odra River system through 4 years suggest that metal pollution decreased, especially for Zn, Pb and Cu. Among all metals studied in the Odra River sediments, substantial reductions of Cd contamination were observed neither in the period after ’97 flood, nor if compared with the earlier results obtained before ’97. No essential differences of the metal contents were observed among the samples for the same river compartment, from the same locality, taken within the five sampling campaigns. The pattern of spatial and vertical metal distributions in the river solids indicates that a variety of sources might be responsible for the contamination; very intensive, historical and current mining and smelting activities probably are the most important ones.     

Effects of metals on the behaviour and oxygen consumption of the mud snail

The behaviour and oxygen consumption rates of adult mud snails, exposed to five metals individually (arsenic, cadmium, copper, silver and zinc) and to one combination of two metals (cadmium and copper), have been examined. The oxygen uptake of distressed and retracted snails was found to be lower than that of controls after exposure to all individual metals except cadmium, which resulted in an elevation of oxygen consumption. The combination of copper and cadmium resulted in a lower rate than either metal alone.     

The Contribution of Ecdysis to the Fate of Copper, Zinc and Cadmium in Grass Shrimp, Palaemonetes pugio Holthius

Depuration through ecdysis by grass shrimp, Palaemonetes pugio, was examined by exposure to a sublethal mixture of copper, zinc and cadmium for 72 h, followed by placement in uncontaminated water to molt. Percent eliminated with the exuviae varied for each metal; of the total intermolt body burden, 11% Cu, 18% Zn and 26% Cd was associated with the exuviae. Cu concentrations of intermolt exoskeletons were significantly higher than of the exuviae of post-ecdysis shrimp suggesting that Cu contained in the exoskeleton was reabsorbed before molting. Exuvial Cd concentration was not significantly different than the concentration of the intermolt exoskeleton, suggesting that most Cd in the exoskeleton was depurated with the exuviae. Although Zn whole-body burdens were lower after a molt, Zn losses were most likely due to excretion because exuvial concentrations were significantly lower than in the intermolt exoskeleton. Cu, Cd and Zn concentrations in exuviae shed in metal-enriched water were significantly higher due to adsorption than exuviae produced in uncontaminated water.     

Heavy metal distribution in Newark Bay sediments

Bottom sediments have been analysed from Newark Bay, New Jersey, for zinc, lead, cadmium, and mercury. The bottom sediment analyses show that the bay sediments are enriched over background levels up to 65 times for zinc, 128 times for lead, 180 times for cadmium, and 155 times for mercury. Analyses of the metal distribution and of available tidal hydraulic data indicate the metal concentrations are due to a combination of source and tidal hydraulics. Dye tracer experiments gathering Lagrangiantype data appear to yield the best result in the investigation of metal trasport phenomena.     

The influence of diet on comparative trace metal cadmium,copper and zinc accumulation in Thais clavigera (Gastropoda: Muricidae) preying on intertidal barnacles or mussels

The influence of diet on comparative metal accumulation was investigated using a predatory muricid gastropod Thais clavigera. Individuals were fed for up to 56 days on either barnacles, i.e., Tetraclita squamosa, or mussels, i.e., Perna viridis, collected from metal-contaminated and clean sites. Barnacles and mussels have contrasting metal handling strategies and, therefore, different body concentrations, intracellular distributions and detoxification systems. Field collection of prey items that accumulated body metal concentrations over a lifetime of exposure allowed bioavailability to the predator, T. clavigera, to be assessed naturally, which may not be the case for prey exposed to metals for a short time in the laboratory. T. clavigera that was fed cadmium- and copper-contaminated barnacles or mussels ingested significantly greater amounts compared to those fed conspecifics collected from clean locations. T. clavigera body cadmium and copper concentrations were not, however, significantly different between individuals fed either contaminated or clean prey. Amount of zinc ingested was similar in mussels collected from clean and contaminated environments but much less when compared to the barnacle prey. The body concentrations of zinc in T. clavigera fed mussels collected from both sites fell. In contrast, the amount of zinc ingested from barnacle prey was significantly greater from those collected from the metal-contaminated site as compared to the clean one. This was reflected as significantly greater body zinc concentrations in T. clavigera fed contaminated barnacles compared to those fed clean individuals. Copper and zinc accumulation from prey was, therefore, complex. It varied between metal and between prey type, but appeared to be related to the amount ingested and the metal handling strategy of the prey.     

Experimental Approach to Cadmium Effects on a Marine Protozoan Community Untersuchungen zum Einfluß von Cadmium auf eine marine Protozoen-Gemeinschaft

The effects of cadmium on a marine protozoan community were studied. After 96 h (0.5 mg/L cadmium) there was a reduction of biomass and a dissappearance of bacterivorous ciliates that were replaced by small flagellates. Other cadmium concentrations utilised affected abundance and biomass after 48 hours. A change of the community structure by the loss of Cd-sensible species and the appearance of Cd-resistant species occurred. The structure of community was simplified and the diversity and variety values decreased. The bacterivore-detritivore and photoautotroph groups, that were the main components in the control, were notably reduced in the presence of cadmium. The metal concentrations on the protozoan biomass increased during the experiment, indicating a certain bioassimilative role of these organisms.     

Heavy metals in marine nematodes: Uptake,tissue distribution and loss of copper and zinc

The uptake and loss of copper and zinc was studied in two species of marine nematode from a non-polluted site and in one species from a polluted site. Copper and zinc concentrations were measured during and after accumulation from seawater in six different tissues of the nematodes. Most of the metal taken up was found to be associated with the cuticle and with a group of tissues including the hypodermis. The importance of the different tissues in heavy metal metabolism by the nematodes is discussed together with the possible routes of uptake of the metals into the animals.     

The contribution of ecdysis to the fate of copper, zinc and cadmium in grass shrimp, Palaemonetes pugio Holthius

Depuration through ecdysis by grass shrimp, Palaemonetes pugio, was examined by exposure to a sublethal mixture of copper, zinc and cadmium for 72 h, followed by placement in uncontaminated water to molt. Percent eliminated with the exuviae varied for each metal; of the total intermolt body burden, 11% Cu, 18% Zn and 26% Cd was associated with the exuviae. Cu concentrations of intermolt exoskeletons were significantly higher than of the exuviae of post-ecdysis shrimp suggesting that Cu contained in the exoskeleton was reabsorbed before molting. Exuvial Cd concentration was not significantly different than the concentration of the intermolt exoskeleton, suggesting that most Cd in the exoskeleton was depurated with the exuviae. Although Zn whole-body burdens were lower after a molt, Zn losses were most likely due to excretion because exuvial concentrations were significantly lower than in the intermolt exoskeleton. Cu, Cd and Zn concentrations in exuviae shed in metal-enriched water were significantly higher due to adsorption than exuviae produced in uncontaminated water.     

Uptake of zinc,lead and cadmium by young whiting in the Severn Estuary

First year whitings, winter residents of the Severn Estuary, had highest levels of zinc in November 1975 but maximum concentrations of lead and cadmium in March 1976. These metal levels are linearly related to both the length and weight of the fish. It is suggested that zinc concentrations reach an upper threshold limit beyond which there is no further accumulation. This is quickly reached as fish move into polluted areas.     

Spatial and temporal variations in cadmium concentrations and burdens in the Pacific oyster (Crassostrea gigas) sampled from the Pacific north-west

Oysters from the north-west coast of Canada contain high levels of cadmium, a toxic metal, in amounts that exceed food safety guidelines for international markets. A first required step to determine the sources of cadmium is to identify possible spatial and temporal trends in the accumulation of cadmium by the oyster. To meet this objective, rather than sample wild and cultured oysters of unknown age and origin, an oyster “grow-out” experiment was initiated. Cultured oyster seed was suspended in the water column up to a depth of 7 m and the oyster seed allowed to mature a period of 3 years until market size. Oysters were sampled bimonthly and at time of sampling, temperature, chlorophyll-a, turbidity and salinity were measured. Oyster total shell length, dry tissue weights, cadmium concentrations (μg g⁻¹) and burdens (μg of cadmium oyster⁻¹) were determined. Oyster cadmium concentrations and burdens were then interpreted with respect to the spatial and temporal sampling design as well as to the measured physio-chemical and biotic variables. When expressed as a concentration, there was a marked seasonality with concentrations being greater in winter as compared in summer; however no spatial trend was evident. When expressed as a burden which corrects for differences in tissue mass, there was no seasonality, however cadmium oyster burdens increased from south to north. Comparison of cadmium accumulation rates oyster⁻¹ among sites indicated three locations, Webster Island, on the west side of Vancouver Island, and two within Desolation Sound, Teakerne Arm and Redonda Bay, where point sources of cadmium which are not present at all other sampling locations may be contributing to overall oyster cadmium burdens. Of the four physio-chemical factors measured only temperature and turbidity weakly correlated with tissue cadmium concentrations (r² = −0.13; p < 0.05). By expressing oyster cadmium both as concentration and burden, regional and temporal patterns were demonstrated, which may have been missed if just concentration was determined.     

MELIMEX,an experimental heavy metal pollution study: Behaviour of heavy metals in an aquatic food chain

Phytoplankton, periphyton and zooplankton samples, chironomid andSialis sp. larvae, and fry of trout and bream collected from unpolluted and artificially metal-polluted limno-corrals were analyzed for mercury, copper, cadmium, zinc and lead. The results indicate that these metals are not accumulated through the food chain and suggest that increased metal concentrations in the environment favor the growth of phytoplankton organisms with a low metal sorption capacity.