Preliminary studies on the leaching of some trace metals from kitchen faucets

Preliminary studies were carried out on the leaching of copper, zinc, chromium, cadmium and lead from eight kitchen faucets by samples of raw, filtered and distributed Ottawa water, a sample of well water and deionized water containing 2 mg l⁻¹ aqueous fulvic acid. Leaching was effected by allowing the test solutions to stand in the inverted faucets for two successive 24-h periods. Concentrations of the metals found in the leachates were copper: first leaching, 0.12–28.0 mg l⁻¹, second leaching, 0.08-3.54 mg l⁻¹; zinc: first leaching, 0.13-10.25 mg l⁻¹, second leaching, 0.06-2.85 mg l⁻¹; chromium: first leaching, < 1.0 × 10⁻³ − 0.395 mg l⁻¹, second leaching, < 1.0 × 10⁻³−0.032 mg l⁻¹; cadmium: first leaching, < 0.05 × 10⁻³−0.01 mg l⁻¹, second leaching, < 0.05 × 10⁻³−4 × 10⁻³ mg l⁻¹; and lead: first leaching, < 0.2−110.0 mg l⁻¹, second leaching, < 0.2−82.0 mg l⁻¹. The faucets containing lead-soldered copper joints released high concentrations of lead, particularly in the case of leaching with the aqueous fulvic acid solution. Under the conditions of the present investigations it is indicated that in some cases the concentrations of metals leached could lead to intakes in excess of the maximum permissible limits for these metals. However, further investigations will be required to determine the possible contribution of these faucets to metal intake under normal usage.     

Removing metals from waste solutions with low rank coals and related materials

Ion exchange media were produced by contacting brown coal, peat or wood sawdust with a solution of calcium hydroxide, preferably as an aqueous slurry of lime. The resultant calcium loading on the media, which ranged up to 8% for sawdust, 12% for peat and to 19% for brown coal, was exchanged for many metals in solution.Preliminary work showed the method to be amenable to extraction of copper, nickel, chromium, cadmium, lead, zinc, mercury, cobalt, silver, iron, manganese, vanadium, germanium, gallium, aluminium, antimony and uranium. For most of the metals more than 99% was removed from I g 1⁻¹ solutions.In more detailed work, confined to calcium loaded brown coal and solutions having metal concentrations more typical of industrial operations, minimum residual metal concentrations of 0.0005 mg l⁻¹ mercury; 0.02 mg 1⁻¹ copper; 0.02 mg 1⁻¹ zinc; <0.05 mg l⁻¹ cadmium; 0.1 mg 1⁻¹ lead and 0.2 mg l⁻¹ manganese were obtained. These results compare favourably with those reported for other relevant processes and there might be operational advantages in the method.The method can be applied either by agitating the calcium loaded media in the solution and then filtering, or by passing the solution through packed beds of the media. Where appropriate, dilute solutions can be up-graded for re-use by stripping the metals from the media which can also be re-used. Alternatively, the loaded media can be combusted and the metals recovered from the residues.The method might be applicable to mine drainage and to effluents from metallurgical processing and electroplating, but more work is required to assess costs.It is suggested that the method is environmentally preferable to other common effluent treatment procedures because it enables collection and recycling of heavy metal pollutants.     

Effect of copper and hexavalent chromium on the specific growth rate of ciliata isolated from activated-sludge

After growing mass and monoxenic cultures of three species of Ciliata (Vorticella microstoma, Colpidium campylum, and Opercularia sp.) with Alcaligenes faecalis as the sole protozoan food, and confirming that copper and hexavalent chromium did not affect the bacterial growth, the effect of these metals on the specific growth rate of each protozoa was examined. The term IL_m (median inhibitory limit) was used to define the metal concentration required to reduce the specific growth rate of protozoa to one-half of that of a control. The IL_m for copper was: 0·25 mg 1⁻¹ (V. microstoma), 0·32 mg 1⁻¹ (C. campylum), and 0·27 mg 1⁻¹ (Opercularia sp.). Regarding hexavalent chromium, IL_m for V. microstoma, C. campylum, and Opercularia sp. were 0·53, 12·9 and 20·2 mg 1⁻¹, respectively. Acclimation of each protozoa to these metals for 96 h resulted in IL_m enhanced values of 1·2–2·2 times as large as that for the control.     

High-rate overland flow

Recommended loading rates for treating raw domestic wastewater by overland flow are 6.3–15 cm wk⁻¹. Information provided in the literature yields little insight regarding the upper range of hydraulic loading rates that could be effectively treated by overland flow. Therefore, field investigations were conducted to evaluate the performance of the overland flow system at overland flow rates from 0.95 m³ day⁻¹ m⁻¹ width of slope (13 cm wk⁻¹ to 4.15 m³ day⁻¹ m⁻¹ (57 cm wk⁻¹).Preliminary treated municipal wastewater was pumped to overland flow slopes, each approx. 3.7 m wide and 36.5 m long. The slope of each plot was 2.5%. The cover crop consisted of a mixture of ryegrass, bluegrass and fescue grass. The plots were operated for 2 years at six different hydraulic loading rates.Effluent BOD₅ concentration averages varied from 6 to 11 mg l⁻¹. The reduction of influent BOD₅ concentration ranged from 87 to 93%. Mean effluent suspended solids values were from 6 to 9 mg l⁻¹ with reductions of influent concentrations of 91–95%. Hydraulic application rate had little effect on percent BOD₅ or suspended solids removal.Total phosphorus reductions were minimal at all hydraulic application rates due to limited soil water contact.Ammonia concentration in the effluent ranged from 1 mg l⁻¹ NH₃-N at the 0.95 m³ day⁻¹ m⁻¹ (13 cm wk⁻¹) applied flow rate of 11.7 mg l⁻¹ NH₃-N at the 4.15 m³ day⁻¹ m⁻¹ (57 cm wk⁻¹) loading rate. Ammonia and nitrogen reductions decreased as the applied flow rate increased. Consequently, lower overland flow rates are necessary for nitrogen removal.The use of high-rate overland flow could potentially reduce the land necessary for this form of land application, if nutrient removal was not a local concern.     

Automated chemical analysis for measuring microgram levels of organic carbon in potable waters

An automated method for the direct determination of microgram levels of organic carbon in potable waters is described. The technique is that of continuous flow analysis and utilizes an automatic sampler, a multiple channel proportioning pump, and an appropriate analytical system (manifold). Samples are acidified, oxygen segmented and passed through a heated inorganic carbon stripper. The stripped liquid is resampled, mixed with silver peroxydisulphate solution and digested at 70°C. The liberated CO₂ is measured by means of infrared photometry. Complete inorganic carbon removal was not possible. From a 30 mg dm⁻³ inorganic carbon solution 0.1% residual remained after stripping. Using a sample volume of 6.3 cm³ min⁻¹, full-scale recorder deflection could be obtained for a 1 mg dm⁻³ organic carbon standard solution with a relative standard deviation of 0.9%. The lower detection limit of practical significance is 50 μg dm⁻³ organic carbon. The analysis rate is 20 samples per hour. Certain synthetic organic materials resisted complete oxidation and included the amino acids glycine, 1-alanine, leucine, iso-leucine and valine.     

Effects of inhibitors on nitrification in a packed-bed biological flow reactor

The individual effect of trivalent arsenic, hexavalent chromium and fluoride on nitrification is studied under continuous load in a packed bed biological flow reactor. The results show that Michaelis-Menten rate expression gives the best representation of nitrification data in the absence of inhibitors. However, in the presence of inhibitors, the system follows a non-competitive mode of inhibition with the following rate expression: The values of V_max and K_s are estimated as 1.466 mg l⁻¹ min⁻¹ and 2.349 mg l⁻¹ respectively. The inhibitor constant K_i is evaluated as 273 mg l⁻¹ for trivalent arsenic, 56 mg l⁻¹ for hexavalent chromium and 1185 mg l⁻¹ for fluoride.     

Simultaneous bioaccumulation of multiple metals from electroplating effluent using Aspergillus lentulus

Toxic impacts of heavy metals in the environment have lead to intensive research on various methods of heavy metal remediation. However, in spite of abundant work on heavy metals removal from simple synthetic solutions, a very few studies demonstrate the potential of microbial strains for the treatment of industrial effluents containing mixtures of metals. In the present study, the efficiency of an environmental isolate (Aspergillus lentulusFJ172995), for simultaneous removal of chromium, copper and lead from a small-scale electroplating industry effluent was investigated. Initial studies with synthetic solutions infer that A. lentulus has a remarkable tolerance against Cr, Cu, Pb and Ni. During its growth, a significant bioaccumulation of individual metal was recorded. After 5 d of growth, the removal of metals from synthetic solutions followed the trend Pb²⁺ (100%) > Cr³⁺ (79%) > Cu²⁺ (78%), > Ni²⁺ (42%). When this strain was applied to the treatment of multiple metal containing electroplating effluent (after pH adjustment), the metal concentrations decreased by 71%, 56% and 100% for Cr, Cu and Pb, respectively within 11 d. Based on our results, we propose that the simultaneous removal of hazardous metals from industrial effluents can be accomplished using A. lentulus.     

Effects of manganese, copper and lead on Selenastrum capricornutum and Chlorella stigmatophora

Algal assays were conducted to observe the responses of Selenastrum capricornutum and Chlorella stigmatophora to the metals manganese, copper and lead, added singly or in combination to both artificial media and natural waters. A 50% reduction in the total algal cell volume of Selenastrum in standard algal assay medium (SAAM) occurred by the addition of either 3.1 mg manganese 1⁻¹ 85 μg copper 1⁻², or 140 μg lead 1⁻¹. For Chlorella grown in 28 ppt artificial seawater plus full SAAM nutrients, the corresponding numbers were 50mg manganese 1⁻¹, 70 μg copper 1⁻¹ or 700 μg lead 1⁻¹. Of the metals tested, only lead was found in higher concentrations in urban and agricultural runoff than at least one of these levels.Theoretical considerations show that a product model is a more reasonable reference for no-interaction than an additive model for experiments in which toxic metals are added in combination. Combination experiments, in which any combination of the three metals act at the same time, indicate (1) synergism between manganese and copper, (2) antagonism between manganese and lead, and (3) antagonism between copper and lead. As to the manganese-lead interaction, it is shown that the lead-induced inhibition of cell division is offset, partially for Selenastrum and completely for Chlorella by the addition of manganese.     

Removal of heavy metals from electroplating rinsewaters by precipitation, flocculation and ultrafiltration

Chromium, nickel, copper and zinc can be effectively removed from electroplating rinsewaters by hydroxide precipitation, flocculation and ultrafiltration. Prior to precipitation, chromium is reduced from the hexavalent to the trivalent form by ferrous sulfate and cyanide in copper and zinc rinsewaters are oxidized by sodium hypochlorite. Minimum metal concentrations in the permeate from separate batches of chromium, nickel, copper and zinc rinsewaters were found to be, respectively, 0.17 mg 1⁻¹ Cr (T), 0.26 mg 1⁻¹ Ni, 0.30 mg 1⁻¹ Cu and 1.84 mg 1⁻¹ Zn. These solubilities are in good agreement with the theoretical solubility curves, except for copper where the formation of stable copper cyanide complexes appears to increase the solubilities at least two orders of magnitude relative to those predicted on the basis of the equilibrium constants for copper hydroxides and oxides. A simple mass balance model, assuming concentrate recycle and constant metal concentration in the permeate, is adequate for the prediction of feed and permeate concentrations as a function of the volume filtered up to a relative volume of about 0.3. Above this value, the feed concentrations are lower than predicted, apparently because of entrapment of metal precipitate in the strainer. Water recoveries are strongly dependent on the specific metal removed and are found to be 24% for Ni with a 0.20 μm membrane, 10% for Cr with a 0.80 μm membrane, 6.5% for Cu and 3.7% for Zn, both with a 0.45 μm membrane.     

The influence of heavy metals on a mixed bacterial population of sewage origin in the chemostat

A reproducible mixed continuous bacterial population has been cultured in the chemostat at a low dilution rate. Four species originally isolated from activated sludge were used to provide an inoculum. The influence of cadmium, chromium, copper and lead as shock doses has been examined at concentrations of 50 mg l⁻¹ and the response of the population was found to vary for each metal. The most toxic metal was copper followed by cadmium, lead and chromium. Continuous doses of chromium and lead have been studied, the latter over a range of concentrations. It appears that concentrations of lead as low as 5 mg l⁻¹ cause modifications in the individual population sizes. Some of the species studied were found to be more resistant to heavy metal toxicity than others.     

Removal of poliovirus and rotavirus from tapwater by a quaternary ammonium resin

A quaternary ammonium-type anion exchange resin was tested as a contact water viral disinfectant. Suspensions of tapwater containing approx. 10⁴ plaque-forming units ml⁻¹ of poliovirus type 1 and Simian rotavirus SA-11 were passed through 1 ml beds of resin, at flow rates of 10–12 ml min⁻¹. With resin 14-1.91 − > 99.9% of the input virus was removed. The beds were effective in removal of virus even after passage of 1500 ml of tapwater. Less than 10% of the virus associated with resin 14-1 could be recovered as compared to 100% for control resin. Kinetic studies indicated that virus adsorbed to the resins were being inactivated.     

The effect of surfactants on the extraction-atomic absorption spectrophotometric determination of copper, iron, manganese, lead, nickel, zinc cadmium and cobalt

Nine surfactants representing pure cationic, anionic and non-ionic detergents, three industrially prepared detergents. sodium pyrophosphate. sodium tripolyphosphate, and a soap were investigated for their effect on the extraction-atomic absorption spectrophotometric determination of copper. iron, manganese and lead. Some results are also given for nickel, zinc, cadmium and cobalt. Cations were extracted into 10 ml of MIBK as APDC chelates. To Avoid emulsion formation, maximum concentration of LAS was 1 mg 1⁻¹, and for formulated and non-ionic detergents and washing powders it was 5 mg 1⁻¹.A standard addition procedure was used to obtain correct results for copper and nickel. Two extractions of iron, cobalt and lead, and one extraction of manganese, zinc and cadmium gave a recovery of 100 ± 5%. Soap gave high recoveries for iron and copper. NTA in concentrations up to 25 mg l⁻¹ did not interfere. EDTA in concentrations up to 25 mg l⁻¹ interfered with iron and nickel determinations, but the addition of 3 mg of aluminium removed the EDTA interference in the determination of copper, manganese, lead, zinc, cadmium and cobalt.For the determination of trace metals in polluted natural waters the amount of 4% APDC was increased to 10 ml and for manganese to 25 ml. An addition of 3 mg aluminium as nitrate after the addition of buffer with subsequent 20 min reaction time is required for the determination of all eight metals by the recommended procedures. The effect of humic acid was also investigated.     

Zinc, cadmium and lead in water, sediments and submerged plants of the Derwent Reservoir, Northern England

A partial budget is presented of the zinc, cadmium and lead entering the Derwent Reservoir. The mean levels in the water column upstream of the site of inflow are: Zn, 0.216 mg 1⁻¹ ; Cd, 0.003 mg 1⁻¹; Pb, 0.065 mg 1⁻¹; the levels after passage through the 4.1 km² reservoir fall by: Zn, 70.3%; Cd, 98.3%; Pb, 89.2%. Most of these metals are deposited in sediments, the mean values for which are: Zn, 1035 μg⁻¹; Cd, 13μg⁻¹; Pb, 827μg⁻¹. Lead, a higher percentage of which occurs as particulate material, is deposited more rapidly than zinc; this effect is especially obvious when streaming of colder water along the bottom of the reservoir takes place at the time of floods. Macroscopic plants are only occasional in this reservoir, due perhaps in part to heavy metal toxicity. Of the two most common submerged species, Nitella flexilis probably accumulates almost all of its metal content directly from the water, but the data suggest that sediments are a source of some of the heavy metals accumulated by Glyceria fluitans.     

A quantitative investigation of the reaction of ozone with p-toluenesulfonic acid in aqueous solution as a model compound for anionic detergents

The reaction of ozone with p-toluenesulfonic acid (PTA) at initial pH 3 and 12 in aqueous solutions (25°C) has been studied at initial concentration 1 mmol l⁻¹ and ozone dose is 24 mg min⁻¹ 1. and 11 mg min⁻¹ 1. respectively. The substrate elimination follow a zero order rate law. A 98% p-toluenesulfonic acid reduction requires at least 7 mol O₃ per mol PTA, however to remove 100% PTA the consumption of ozone increases to 16 mmol O₃ per mmol PTA. At this point a 28% reduction of DOC and a 74% COD reduction was achieved.The PTA decomposition is quicker at higher ozone flow rate, but the specific ozone consumption increases also. As oxidation products the following compounds were identified and their quantitative variations as function of ozonation time were measured: methylglyoxal, acetic acid, formic acid, pyruvic acid, oxalic acid, H₂SO₄ and H₂O₂. As byproduct mesoxalic acid was identified. At pH 12 lactic acid as a further oxidation product was observed.Balances of carbon, sulfur and methyl as well of the acid equivalents indicate one or more intermediates with a sulfonic acid group. These intermediates with a proportion of about 20% disappear after 100% PTA elimination. On account of these results a reaction mechanism is discussed.     

Investigations on natural Hungarian zeolite for ammonia removal

Use of natural zeolites deposited at Tokaj mountain, Hungary, for ammonia removal from synthetic and municipal wastewaters was studied. The optimal ion exchange conditions found were as follows: Na-form clinoptilolite, 0.5–1.0 mm in particle size and about 5–7 BV h⁻¹ loading rate. Using synthetic wastewater in the column of 9.5 cm i.d. × 92 cm, about 4.50 mg NH₃-N g⁻¹ clinoptilolite ammonia breakthrough capacity was achieved. For regeneration of the ion exchange bed, 10–20 BV of regenerant were necessary to remove the 98–99%, of ammonia with flow rate of a 5–7 BV h⁻¹.     

Effects of mixing velocity on anaerobic fixed film reactors

Four laboratory-model upflow anaerobic fixed film reactors (AFFR 1, 2, 3 and 4) treating landfill leachate were subject to identical volumetric organic load (7 kg COD m⁻³ d⁻¹) and hydraulic retention time (3d), but the contents in each unit were continuously recirculated for 10 months at four different velocities, respectively, of 21, 66, 680 and 3063 cm h⁻¹. The objective was to assess the effects of such mixing velocities (ν) on COD removal efficiencies (E), mean cell residence time (MCRT) and substrate utilization rate (U expressed as g COD removed d⁻¹ g⁻¹ VSS). The results showed that the relationships between E and ν and MCRT and ν were inverted U-shaped curves. The two middle reactors (AFFR 2 and 3) had near-optimum velocities (ν₂ and ν₃) with maximum E values of 88–89%. AFFR 4 had a high value of ν scouring biofilm on the biorings, resulting in higher concentrations of SS, VSS and COD in the effluent. All four reactors had nearly similar values of U (1.85–2.14 g COD d⁻¹ g⁻¹ VSS). The value of ν₁ (AFFR 1) was too low to enhance performance and ν₄ was too high to retain the biomass. The optimum recycle velocity, under the test conditions, was in the range of 66–680 cm h⁻¹.     

An automated procedure for the determination of total Kjeldahl nitrogen

A procedure for the determination of total Kjeldahl nitrogen in surface fresh waters and organic wastes is described. Organic nitrogen compounds are converted to ammonium sulphate by a catalytic (red mercuric oxide) acid-sulphate digestion. The digest time is 3 h and allows for a maximum of 36 samples, 2 blanks and 2 standards to be processed simultaneously. There is no pH adjustment required following the digestion. Calibration curves covering the ranges (i) 0.5–100 μg NH₃---Nl⁻¹ and (ii) 10–1000 μg NH₃---Nl⁻¹ were linear within ±2%. The detection limit of the method is 0.5 μg TKNl⁻¹. The concentration range of TKN for which the method is suitable is 0.5 μg Nl⁻¹–40 mg Nl⁻¹. The method displayed a high tolerance to interferences from copper, iron, mercury and hardness. Digest procedure gave a high recovery and reproductibility over a wide range of nitrogen compounds tested.     

Environmental chemistry of copper in Lake Monona, Wisconsin

Lake Monona, located at Madison, Wisconsin, received over 1.5 × 10⁶ pounds of copper sulfate in the past 50 yr to control excessive algal growth. Dissolved copper on Lake Monona epilimnion is inversely related to pH which indicates possible control of dissolved copper by basic copper carbonate. Concentrations as high as about 4 μg Cu l⁻¹ were found in Lake Monona epilimnion, which also contains 3.3 me l⁻¹ (milliequivalents per liter) of alkalinity, mostly bicarbonate. Concentrations of dissolved copper were consistently lower (0.3 μg Cu l⁻¹) in the hypolimnion. Sulfide probably controls dissolved copper in the hypolimnion during anoxic conditions because of sulfide insolubility. Particulate copper concentrations of about 3 μg l⁻¹ increased slightly with depth. The highest concentrations of copper in Lake Monona sediments (650 mg kg⁻¹) were found approximately 60 cm below the current sediment surface. Surface sediments of Lake Monona contained approximately 250 mg Cu kg⁻¹ sediment dry weight.     

An in situ method to compare the potential for periphyton productivity of lotic habitats

A simple field method for measuring relative net productivity in flowing waters is described. To assess its sensitivity and practicality, the eutrophication potential of a tertiary sewage treatment plant effluent was assayed on the Fort River of Amherst, Massachusetts. Two sets of three 10 m lexan tubes (1.25 cm i.d.) were anchored to the river bed 100 m upstream and downstream from the sewage plant outfall. Data collection began following a 2 week colonization period for the periphyton community. Substrate primary productivity (mg O₂ min⁻¹) was determined by subtracting inflow dissolved oxygen concentrations from these levels at the discharge ends of each tube and multiplying the difference by the flow rate. The downstream tubes demonstrated an enhanced response at a 0.01 level of significance to an increment of 0.005 and 0.1 ppm of phosphorous and nitrogen respectively. Data analysis revealed a highly significant regression of the net productivity on stream flow which was adjusted for by an analysis of covariance. The productivity of the downstream station was distinctly higher (0.4522 mg O₂ min⁻¹) then the value of the upstream station (0.2584 mg O₂ min⁻¹). The protocol thus affords a biological summation of the sewage effluent through comparison with the control station replicates.     

Mutagenicity and organic solute recovery from water with a high-volume resin concentrator

The high-volume sampler achieves an average 70% organic removal with four 1150 ml columns, from a 100–2001, waste-water or potable water sample pumped at 200 ml min⁻¹ and 8000–10,000 kN m⁻². Sample elution yields composite resin concentrates which are mutagenic to Salmonella typhimurium strains TA98 and TA100. No mutagenicity is observed in concentrator effluents or in blanks between samples. The main advantage of the resin concentrator is in savings of time and solvent for a large sample volume. Recoveries of spikes of compounds taken from the EPA priority pollutant list are reported.