Storm water runoff measurements of copper from a naturally patinated roof and from a parking space. Aspects on environmental fate and chemical speciation

Release of copper from a naturally aged copper roof on a shopping centre building in a suburban site of Stockholm has been measured during different rain events after its interaction with the internal drainage system and storm drains made of cast iron and concrete. Concentrations of copper removed by means of urban storm water from a nearby parking space have been determined for comparison. Predictions and measurements of the chemical speciation of released copper are discussed compared to the total concentration, and to threshold values for freshwater and drinking water.The results clearly illustrate that the major part of the released copper from the roof is readily retained already during transport through the internal drainage system of the building, a pathway that also changes the chemical speciation of released copper and its bioavailable fraction. Most copper, not retained by cast iron and concrete surfaces, was strongly complexed to organic matter. The median concentration of free cupric ions and weak copper complexes was less than, or within the range of reported no effect concentrations, NOECs, of copper in surface waters. The parking space contributed with significantly higher and time-dependent concentrations of total copper compared to measured concentrations of copper from the roof after the interaction with the drainage system. Most copper in the surface runoff water was strongly complexed with organic matter, hence reducing the bioavailable fraction significantly to concentrations within the NOEC range. Dilution with other sources of urban storm water will reduce the released concentration of copper even further.The results illustrate that already the internal drainage system and the storm drains made of cast iron and concrete act as efficient sinks for released copper which means that any installation of additional infiltration devices is redundant.     

Aspects of water quality and the toxicity of copper to rainbow trout

Studies were made of the effects of additions of a sewage effluent, an amino acid, humic substances, and suspended organic matter on the acute lethal toxicity of water containing copper sulphate to rainbow trout. In all cases the toxicity of a given total concentration of copper was quantitatively reduced. It was concluded that neither the total concentration of copper nor that of “soluble” copper in a water could be used to determine the toxicity to fish which was attributable to copper. It was also concluded that data from toxicity tests with copper in which natural surface waters are used for dilution purposes cannot define the true toxicity of copper or have application to other natural waters except when the concentrations of the toxic chemical species are known.     

Copper/bicarbonate equilibria in solutions of bicarbonate ion at concentrations similar to those found in natural water

The equilibrium constant for the reaction between cupric and bicarbonate ions which results in the formation of the soluble complex species, CuCO₃, was determined by means of a cupric ion selective electrode. The possibility of the formation of complex species other than CuCO₃, was examined. The implications of the presence of the CuCO₃ species to the toxicity of copper to fish in natural waters are discussed.     

Silver complexation in river waters of central New York

The dissolved component of the apparent silver complexation capacity was determined for Susquehanna and Chenango River water samples collected over a 3-month period in the vicinity of Binghamton, New York. Silver ion activities detected by the Ag⁺/S^2? ion selective electrode during potentiometric titration of the river water with AgNO₃ were lower than Ag⁺ activities calculated with an inorganic equilibrium speciation model. The maximum difference in Ag⁺ activity, which ranged from 1.5 × 10^?8 to 8.4 × 10^?8, was attributed to the presence of a constituent or constituents in the river water which strongly bind Ag, perhaps dissolved organic matter and/or colloidal material. Variation in apparent complexation capacity between river water samples was explained by different concentrations of the ligands complexing Ag. A tentative extrapolation of the dissolved Ag speciation to Ag concentrations in natural river water suggested that most of the Ag would be complexed by Cl^? and an unidentified constituent or constituents.     

Effects of humus concentrations on benzo[a]pyrene accumulation from water to Daphnia magna: comparison of natural waters and standard preparations

The bioaccumulation of benzo[a]pyrene (BaP) into Daphnia magna from two natural humic waters (one lake water and one bog water), and two humus preparations (Nordic Reference fulvic acid (Nordic FA) and a lyophilized concentrate) of the same aquatic origin was measured by using several dissolved organic carbon (DOC) concentrations for each sample. The partition coefficient (Kp) of BaP to the humus content of the water was determined by an equilibrium dialysis technique. In all four samples, an increase in humus concentration decreased the bioavailability of BaP in a logarithmic manner. The Nordic FA and the natural untreated humic water, from the same source as the water used for isolation of Nordic FA, gave a similar DOC bioaccumulation response and similar Kp values. The difference between the two natural humic waters was obvious, both in the accumulation experiments and the Kp values. The assumption that the total bound fraction of organic pollutant is not available for D. magna is not fully supported by this study.     

Determination of the complexing properties of drinking waters toward copper(II) and aluminium(III) by ligand titration

The complexing capacity of some drinking waters for aluminium(III) and copper(II) is determined by a ligand titration with metal ions based on the use of complexing resins. The resins used in the titration are the iminodiacetic resin Chelex 100, the carboxylic resin Amberlite CG50 and the anionic exchange resin AG1X8. They allow the detection of ligands forming complexes of different stability with the metal ions used for the titration, since they have different sorbing properties. After equilibration with the resin, the concentration of the free metal ion in solution is evaluated from the concentration of sorbed metal ion and from the quantity K^*, which is the ratio of the concentration of the metal ion sorbed on the resin to the free metal ion in solution. It strongly depends on the conditions, but it can be evaluated, at the considered conditions, from the sorption equilibria of the metal ion on the resin. The concentration of the ligands in solution and the conditional stability constant are obtained from the Ruzik linearization procedure. Very strong ligands of copper(II) and aluminium(III) were detected in a tap water sample at concentrations ranging from 10⁻⁷ to 10⁻⁶ mol kg⁻¹, and forming complexes having conditional complexation constants K_cI=2.3×10¹⁷ (pH=6.77) and 4.5×10¹⁶ (pH=6.24), respectively, for copper(II) and aluminium(III). Weaker ligands were detected using the less strongly sorbing resins Amberlite CG50 and AG1X8, but at a concentration equal to that of the strong ligands. This was ascribed to the presence of competing metals in solution, not sorbed by the weak resins. Two other drinking waters had completely different complexing properties both towards copper(II) and aluminium(III), containing much weaker ligands.     

Production of lipophilic volatile organohalogen materials during laboratory chlorination of some waste water and polluted river water samples from Yugoslavia

Water chlorination leads to the generation of various halogenated products of natural and waste water organic mater. In natural surface water humic matter usually makes the greatest part of the total organic matter. However, in the river water polluted with various organic wastes, other organic matter is also present in significant concentrations. The investigation of the relationship between the concentration of organic matter in the samples of waste water and heavily polluted river waters in Yugoslavia on one side, and the production of the lipophilic volatile organohalogen materials during the process of their chlorination on the other side is described. The production of the halomethanes and other ECD response materials during the chlorination of water samples in laboratory conditions is compared with the concentrations of organic materials in water samples. From the obtained linear correlation coefficients, possibilities of predicting amounts of organohalides during the chlorination process by using several very simple methods for the organic materials estimation in the investigated water samples are discussed and compared.     

Speciation and rate of loss of copper from lakewater with implications to toxicity

The rates of disappearance of total dissolved copper in six prairie “pothole” hard water lakes treated with copper were measured. The first-order rate constants ranged from 1.01 to 0.11 day⁻¹, and the half-times from 1 to 7 days. Concentrations of 12 inorganic copper species and the humic acid-copper complex were calculated for the pH range of each lake. Less than 0.5% of total dissolved copper was calculated to be present at any time as free cupric ion. The total dissolved concentration of added copper was reduced with time probably through precipitation of tenorite (in some cases malachite) and by adsorption on solids.The effectiveness of copper as an algicide in these lakes at the relatively low concentration of added copper is explained in terms of a “total toxic copper” concept, which includes the species Cu(OH)₂⁰ and CuOH⁺ in addition to cupric ion, the generally recognized toxic species.     

Determination of copper in water by means of chalcocite copper ion-selective electrode

The possibility of determination of copper in natural waters was tested by direct potentiometry with chalcocite copper sensitive ion selective electrode. This can be carried out for the copper concentration down to 6 μg l⁻¹ when the standard additions procedure is used. The electrode characteristics was investigated and as a medium was proposed a TFB solution containing Tris, potassium fluoride and potassium nitrate. However at the extreme low concentrations of copper the water samples after addition of TFB should be heated to boiling. In these conditions the accuracy of determination for the average of five measurements is not worse than 25%, and precision is of the order of 20%.     

Complexation of copper in the effluent of a sewage treatment plant and an estimate of its influence on toxicity to coho salmon

Measurements by cupric ion electrode of the complexing capacity of the effluent from a sewage treatment plant (STPE) averaged 0.300 mg 1⁻¹. Of the complexed Cu 67% was due to compounds of 10,000 MW. Organic compounds removable by activated carbon composed 88% of the total organic carbon and were responsible for 87% of the complexation. Complexation of Cu²⁺ by STPE diminishes the toxicity from total Cu to juvenile coho salmon; the LC₅₀ was 0.164 mg 1⁻¹ for river water vs 0.286 mg 1⁻¹ for 40% STPE. The LC₅₀ of Cu²⁺ was approximately the same (0.017 vs 0.022 mg 1⁻¹) in both matrices; this species thus appears to play a toxic role. The mean survival time in diluted STPE with added Cu was inversely proportional to the Cu²⁺ concentration.     

Complexation analysis of fresh waters by equilibrium diafiltration

Equilibrium ultrafiltration has been employed to determine the extent of Cu, Ni, Co, Fe, Mn and Zu chelation in oxic waters from mineralized terrains. Concentrations of Cu, Ni and Co were determined in different organic fractions separated by various Amicon ultrafilters. Titrations of fresh water samples with metal ions were made, and “free” metal concentration measured by equilibrium diafiltration. Experiments were made at concentrations and pH at which metals and ligands occur in natural waters. Conditional stability functions ranged from 10^6.72 at pH 6.5 to 10^7.07 at pH 7.6 for Ni and 10^6.85 at pH 6.8 to 10^6.97 at pH 7.6 for Co. At low metal concentrations (8 × 10⁻⁷ M) only one complexing class of major importance for natural water environments was observed. The order of metal complexing ability was found to be Cu > Ni > Co > Zn > Mn with Cu showing a preference towards the higher MW organic fractions.     

Correlation of some organic pollution factors in water systems in Northern Greece

The degree of organic pollution in natural waters of northern Greece has been evaluated through measurement of TOC, DO, fluorescence, absorbance and complexing capacity. Additionally certain other parameters were measured like temperature, conductance, hardness, alkalinity and total iron content to get a better idea of the extent of pollution. The results showed that Lake Agios Vasilios was the most heavily polluted. On the other hand the River Loudias has greater organic charge than the River Axios.     

Chemical water quality in Thailand and its impacts on the drinking water production in Thailand

In Thailand, surface water and groundwater are the main water sources for tap water and drinking water production. Thirty-six different samples from surface waters from Chao Praya and Mae Klong rivers, tap waters, bottled drinking waters, groundwaters and commercial ice cubes from around the Bangkok area were collected. Water samples were also taken from two waterworks in the Chonburi province. The extensive survey showed that, overall in all water samples investigated, there was only a minor pollution which could be traced back to the analyses performed including amongst others total organic carbon, inorganics and heavy metals, pesticides, organochlorine compounds, volatile organic compounds, surfactants, pharmaceuticals and disinfection by-products. However, whenever organic micropollutants could be detected in surface water, such as, e.g. the herbicide atrazine, they were also present in the tap water produced thereof proving that the present treatment steps are not sufficient for removal of such pollutants. The concentration of disinfection by-products was higher in tap water produced from Chao Praya river than from Mae Klong river. Disinfection by-products were also found in bottled drinking water. Commercial ice cubes contained anionic surfactants and their metabolites at elevated concentrations. The data of this study constitute the first set of homogenous data for the chemical water quality and also aid development of new water quality criteria in Thailand.     

The toxicity of some forms of copper to rainbow trout

The lethal toxicity of copper to rainbow trout in hard water was found to be related to the total concentration at which soluble copper. Cu²⁻ and CuCO₃, was present in the water, rather than to the concentration of either of these two forms alone. It is suggested that, except in the presence of highly toxic organo-copper compounds, from a knowledge of the cupric ion concn, the pH, and the alkalinity of a water, the total concentration of soluble copper can be calculated and hence the toxicity of that water determined.     

Organically-bound copper in lake and river waters in Japan

Organically-bound copper, organic matter concentrations and molecular weight of the organic matter in lake and river waters at Hokkaido in Japan were measured. The interaction between copper and the organic matter was also investigated by using Sephadex gel. The ratio of organicallybound copper to total copper was 10–70%. There was no relationship between the copper complex and the organic matter. From thermodynamic calculation, it was concluded that the variation of the ratio from 10 to 70% depended on the variation of stability constant of copper with the organic matter. The organic matter has molecular weight of 300–700 which resembles fulvic acid originating in river water.     

The chemistry of cadmium in natural water—II. The adsorption of cadmium on river muds and naturally occurring solids

The adsorption of cadmium on mud solids and particles of clay, silica, humic material and other naturally occurring solids has been studied. Radiochemical methods were employed so that cadmium concentrations in the μg l⁻¹ range could be used. The variation of the extent of adsorption with many of the large number of factors involved was investigated, concentration factors (distribution coefficients) were determined, and in the course of the work, loss of cadmium by adsorption on container surfaces and filters was investigated.Rates of adsorption and desorption were shown to be rapid. Concentration factors for river muds varied between 5000 and 50,000 and depended mainly on the type of solid, its state of subdivision, the concentration of metal ion present, the time of contact and the concentration of complexing ligands. Humic material appeared to be the main component of river mud responsible for adsorption. Adsorption and desorption processes are likely to be major factors in controlling the concentration of cadmium in natural waters and will tend to counteract changes in the concentration of the metal ion in solution.     

Effects of inorganic complexing on the toxicity of copper to Daphnia magna

Effects of carbonate-bicarbonate, orthophosphate, and pyrophosphate on the toxicity of copper (II) to Daphnia magna were studied at constant pH and total hardness. Mortality rates and reciprocal survival times were directly correlated with cupric (Cu²⁺) and copper hydroxy (Cu(OH)n) ion activities as determined by equilibrium calculations. Toxicity was negatively related to activities of soluble copper carbonate (CuCO₃) and other complexes, and was found to be independent of dissolved copper or total copper concentrations.     

Disinfection byproduct formation in reverse-osmosis concentrated and lyophilized natural organic matter from a drinking water source

Drinking water treatment and disinfection byproduct (DBP) research can be complicated by natural organic matter (NOM) temporal variability. NOM preservation by lyophilization (freeze-drying) has been long practiced to address this issue; however, its applicability for drinking water research has been limited because the selected NOM sources are atypical of most drinking water sources. The purpose of this research was to demonstrate that reconstituted NOM from a lyophilized reverse-osmosis (RO) concentrate of a typical drinking water source closely represents DBP formation in the original NOM. A preliminary experiment assessed DBP formation kinetics and yields in concentrated NOM, which demonstrated that chlorine decays faster in concentrate, in some cases leading to altered DBP speciation. Potential changes in NOM reactivity caused by lyophilization were evaluated by chlorination of lyophilized and reconstituted NOM, its parent RO concentrate, and the source water. Bromide lost during RO concentration was replaced by adding potassium bromide prior to chlorination. Although total measured DBP formation tended to decrease slightly and unidentified halogenated organic formation tended to increase slightly as a result of RO concentration, the changes associated with lyophilization were minor. In lyophilized NOM reconstituted back to source water TOC levels and then chlorinated, the concentrations of 19 of 21 measured DBPs, constituting 96% of the total identified DBP mass, were statistically indistinguishable from those in the chlorinated source water. Furthermore, the concentrations of 16 of 21 DBPs in lyophilized NOM reconstituted back to the RO concentrate TOC levels, constituting 86% DBP mass, were statistically indistinguishable from those in the RO concentrate. This study suggests that lyophilization can be used to preserve concentrated NOM without substantially altering the precursors to DBP formation.     

Batch copper ion binding and exchange properties of peat

Cupric ion fixation by raw peat is likely involved in both cation exchange with H⁺, Ca²⁺, Mg²⁺ and adsorption-complexation, i.e. fixation of the same equivalent of copper ions and anions (NO₃⁻) without any ion release. The importance of both reactions depends largely on initial copper concentration, peat type and pH. Isotherms of copper (initial concentration ranging between 1 and 20 mM) fixation on two types of peat (eutrophic and oligotrophic peat at 30 g d.w./l at pH ranging between 2 and 4) showed that the higher the initial cupric concentration, the more important is this complexation reaction; over this initial cupric concentration range, ion exchange sites were relatively saturated and reached 308 and 101 mmol/kg d.w. for eutrophic and oligotrophic peat whereas no saturation was found for complexation sites, their capacity attaining up to 74 and 119 mmol/kg d.w., respectively.

The apparent equilibrium constant for ion exchange with acid-treated peat (initial pH 4.0, 30 g d.w./l) for various metal binding on both peat sites ranged between 1.1 and 10.8 in 15 mM metallic solutions. The apparent affinity in batch conditions for 5 elements may be compared according to the apparent global equilibrium constants, ranging between 1.1 × 10⁻⁶ and 20.2 × 10⁻⁶: Pb > Cu > Ca > Mg, Zn for eutrophic peat and Pb > Ca > Cu > Mg, Zn for oligotrophic peat.     

Metals in an acid mine stream and estuary

Data on the concentrations of selected metals in the waters and sediments of an acid mine stream and its estuary are reported. The river water at the mouth is enriched in zinc, copper and manganese by at least two orders of magnitude above normal river water concentrations after having been significantly diluted by non-metalliferous tributaries. Iron is precipitated along the length of the stream while losses of copper and zinc from solution occur by adsorption onto hydrated ferric oxide above pH values of 4.5 and 6, respectively. Manganese concentrations are affected solely by dilution. The dissipation of the metalliferous river water in the marine regime is restricted, giving rise to estuarine waters containing high concentrations of copper and zinc both in solution and hydrogenous suspension. Deposition of hydrogenous material within the estuary is small, but approximately 50 % of the zinc and 90 % of the copper in the sediment is in a potentially mobile form. The environment is an unsuitable habitat for all but a few organisms.