Copper (II) Speciation in a Freshwater Ecosystem

Results of chemico-biological experiments in a natural water body with the use of model systems with Cu (II) introduced in them at different proportions of its chemical forms (natural and simulated) in the solution. The model forms used in the experiments were Cu complexes with benzyl- and hexadecylmalonic acids, simulating low-molecular dissolved organic substances. The experimental conditions were chosen based on a preliminary calculation using WATEQ–4f program. The complexes of Cu with hexadecylmalonic acid are found to be absorbed by suspensions and removed into bottom sediment more actively than other Cu forms. The toxicity of introduced Cu for the phyto- and zooplanktonic communities is found to depend on the concentration of Cu²⁺ aqua-ions in the solution, in the presence of which the higher concentrations of complexes with malonic acids do not exert their toxic effect.     

Diurnal and vertical variability of pH, [O2], and Eh in the Novosibirsk water reservoir

In situ data on the daily dynamics of pH, [O₂], and E_h values at five water layer depths were obtained. Some regularities have been established: All these parameters are characterized by significant diurnal fluctuations and their daily cyclic recurrence; the diurnal cycles of pH and [O₂] nearly coincide (they show close extreme points on the time scale); the E_h cycles are less distinct and antisymbatic to the pH and [O₂] cycles, but typical E_h extremes sometimes lag by 2–3 h. These data were analyzed using the principle of equilibrium locality and partiality. The main flows of O₂ and CO₂ in the system have been revealed with regard to the water layer–atmosphere gas exchange, absorption of CO₂ by phytoplankton in the photic layer, breathing of phyto- and zooplankton, birth and die-off of biota, settling of mortomass, and redistribution of detailed components within the water layer as well as between it and the bottom sediments. On the basis of the results obtained, the known technique for estimating the content of primary photosynthesis products (Bruevich's method) was corrected. The used generalized algorithm of chemical thermodynamic analysis of the substance state in aqueous systems can be applied to waters of different classes as well as any surficial waters if E_h, pH, and [O₂] are taken into account.     

Behavior of metals (Cu,Zn and Cd) in the initial stage of water system contamination: Effect of pH and suspended particles

The fate of potentially harmful metals (PHM) after their entry into an unpolluted fresh water body depends on the physicochemical and biological parameters of the aquatic ecosystem. This paper considers the effect of pH and suspended particles (SP) on the behavior of Cu, Zn and Cd when they enter a fresh water reservoir. In a field experiment, four mesocosms were constructed in the Novosibirskoye Reservoir to allow systematic variation of SP concentration (15 or 250 mg/L) and pH (8.5 or 6.5). The initial concentrations of Cu, Zn and Cd in the mesocosms were 1000, 1000 and 200 μg/L, respectively. Natural bottom sediments were used to provide additional mineral SP, and water hyacinth was used as a floating plant species. Over 11 days, measurements were made of several indicators: residual metal concentration in solution ([PHM]_w); metal concentration in SP ([PHM]_s); primary productivity of the phytoplankton community; mass of settled SP; PHM concentration in settled SP; and PHM bioaccumulation by water hyacinth. The ratio [PHM]_w/[PHM]_s in the water varied in the order Cu < Zn < Cd and was higher at pH 6.5 than at pH 8.5. This observation reflects different PHM sorption (Cu > Zn > Cd) onto mineral SP and PHM biosorption by planktonic organisms. Phytoplankton acts as a renewable source of organic SP and plays an important role in metal removal from the water in the mesocosms. After 11 days the residual concentrations of Cu, Zn and Cd in the mesocosm without SP addition (initial SP concentration was 15 mg/L) were 272, 355 and 84 μg/L, respectively. The residual concentrations of Cu, Zn and Cd in mesocosms with SP addition were 57, 100 and 14 μg/L at pH 8.5 and 80, 172 and 20 μg/L at pH 6.5, respectively. Therefore, addition of SP resulted in faster and more complete removal of metals into the bottom sediments. Floating plants (water hyacinth) accumulated PHM (Cu > Zn > Cd) more effectively at pH 8.5 than at pH 6.5, and PHM concentrations in the roots were higher than in settling SP. The general trends of PHM removal from contaminated water via sedimentation and bioaccumulation are compared with changes of metal speciation in solution.