This paper describes an analytical procedure for free estrogens and their conjugates in domestic wastewater. The procedure demonstrated in this study is innovative in terms of levels of detection and quantification of the following substances: estrone (E1); 17beta-estradiol (E2); 17alpha-ethynylestradiol (EE2); estriol (E3); estrone-3-sulfate (E1-S); beta-estradiol 3-sulfate (E2-S); estriol 3-sulfate (E3-S); estrone beta-D-glucuronide (E1-G); beta-estradiol 17-(beta-D)-glucuronide (E2-G); estriol 3-(beta-D)-glucuronide (E3-G); beta-estradiol 3-sulfate 17-glucuronide (E2-SandG); and estradiol 3,17-disulfate (E2-diS). The detection limits of this method ranged from 0.1 to 1.4 ng/l. The recovery efficiencies of the estrogens in the analysis from influent and effluent of the secondary settling tank in a wastewater treatment plant (WWTP) were higher than 94% for the free estrogens, but were less than 50% for the conjugated estrogens. The field study using this method was conducted at twenty WWTPs in Japan. The median concentrations of the estrogens ranged from ND to as high as >100 ng/l. In the influent and secondary effluent samples, the concentrations of E1, E2 and E3 were the same levels as those previously reported. We found that the conjugated estrogens exist at higher concentrations in the influent and the secondary effluent than in the other studies, and that the concentrations of the conjugated estrogens were higher than those of the free estrogens.
Laboratory evaluations were conducted to study the toxic responses of heavy metals such as copper and nickel of an autotrophic culture of strict nitrifiers (Nitrosomonas sp. and Nitrobacter sp.) in continuous flow stirred tank reactors (CSTR). One of the CSTRs was operated as a suspended growth (SG) system while the other was operated as an attached & suspended growth (A&SG) system. Nitrification inhibition in a SG and A&SG systems was investigated with the emphasis on the effect of shock loading of copper and nickel. As a result of the copper and nickel test, Nitrosomonas sp. was found to be equally or more sensitive than Nitrobacter sp. However, a higher influent nickel concentration of 50 mg/L was needed to cause a similar percent inhibition of ammonium oxidation than the copper concentration of 5 mg/L. A geochemical equilibrium speciation model, MINTEQA2/PRODEFA2, was used to compute the concentrations of various chemical species present in the wastewater for both systems. The high correlations of Cu(NH3)4+2 and Ni(NH3)4+2 with percent inhibition were found and it was thought that they were probably the species responsible for the inhibition of ammonia oxidation.
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