Estimation of Zn and Cu unit output loads from animal husbandry facilities.

Zinc (Zn) and copper (Cu) are toxic to aquatic organisms at very low concentrations that do not affect humans. We measured the daily output of Zn and Cu in wastewater from livestock farms to aquatic environments because waste from animal husbandry operations contains high levels of Zn and Cu. At most pig farms in Japan, a mixture of urine, some faeces, and service water is treated in onsite wastewater treatment facilities and discharged into a water body. Some dairy farms also have wastewater treatment facilities. We surveyed 21 pig farms and six dairy farms. The unit (i.e., per head) output load from piggery wastewater treatment facilities ranged from 0.13 to 17.8 mg/head/d for Zn and from 0.15 to 9.4 mg/head/d for Cu. Over 70% of pig farms had unit output loads of Zn and Cu below 6 and 2 mg/head/d, respectively. For dairy farms, the unit output load from wastewater treatment facilities was estimated at 1.8-3.6 mg/head/d for Zn and 0.6 mg/head/d for Cu. The unit output load for Zn from piggery wastewater treatment facilities was similar to that from treatment facilities for human waste. However, pig farms generally raise several thousand to tens of thousands of pigs; pig farms are therefore presumed to be a significant point source of Zn in rural areas.

Ultrasensitive CE for heavy metal ions using the variations in the chemical structures formed from new octadentate fluorescent probes and cationic polymers.

Novel fluorescent probes have been developed for the ultratrace detection of heavy metal ions by capillary electrophoresis using laser-induced fluorescence detection. Based on a molecular design, the probes are composed of an octadentate chelating moiety, a macrocyclic DOTA (tetraazacyclododecanetetraacetic acid) and an acyclic DTPA (diethylenetriaminepentaacetic acid) frame, a spacer and a fluorophore (fluorescein). These were chosen on the basis of their ability to form kinetically inert and highly emissive complexes, and to prevent a quenching effect even with heavy and paramagnetic metal ions. Addition of a cationic polymer, polybrene, in the separation buffer provided high resolution and simultaneous detection of Ca(2+), Mg(2+), Cu(2+), Zn(2+), Ni(2+), Co(2+), Mn(2+), Cd(2+) and Pb(2+). The direct fluorescence detection of these metal ions with high sensitivity at lower ppt levels, typically 2-7 × 10(-11) M (potentially sub-ppt), was successfully achieved. While separation of anionic compounds using a counter cation ("Ion Association (IA)" mode) is typically controlled by the ion association equilibrium constants, K(ass), it was found that differences in the mobilities, µ(ep(IAC)), of the ion association complexes formed between the probe complexes and counter cations are the driving forces for separation in this new method. This suggests that each of the polybrene-probe complexes has different chemical structures among metal ions, which were able to be determined by CD spectra in this investigation. This novel separation mode was termed the "Ion Association Complex (IAC)" mode, distinct from the IA mode.

Direct fluorometric detection of paramagnetic and heavy metal ions at sub-amol level using an aromatic polyaminocarboxylate by CZE: Combination of pre- and on-capillary complexation technique.

The low sensitivity of simple CZE for detecting metal ions is a long-standing problem even when an LIF detection system is employed. We have successfully achieved an ultrasensitive CE-LIF using a simple CZE mode (typical detection limit: 10(-11)-10(-10) mol/dm(3)). Both the design of a newly synthesized ligand and the combination of a precapillary derivatizing technique with an on-capillary ternary complexing technique have enabled us to achieve this extremely low LOD and high resolution of large metal complexes. The direct fluorescent detection of the paramagnetic metal ions was achieved for the first time despite their intrinsic fluorescent quenching nature. The fluorescent ligand (L) consists of a polyaminocarboxylate chelating moiety, a strongly emissive fluorescein moiety and a spacer connecting the two portions. The migration behavior of various metal-L complexes was investigated. The resolution among the complexes was improved by the introduction of a ternary complex equilibrium of the kinetically stable mother complexes with OH(-) ion. The analytical potential of our simple system was examined, and it was proved that the system was one of the most sensitive methods without the need for any preconcentration process.