Cd2+ 이온으로 교환된 제올라이트 Y 단결정은 294 K에서 |Na75|[Si117Al75O384]-FAU(Na75-Y, Si/Al = 1.56)에 0.05 M인 Cd(NO3)2(pH = 3.65)수용액으로 교환하여 723 K에서 진공 탈수를 통해 준 비하였고(crystal 1) 두 번째 결정은 첫 번째 결정과 같이 준비한 뒤 294 K에서 건조된 벤젠을 72시간 동안 노출시켜 준비했다(crystal 2). 이들의 구조는 싱크로트론 X-선을 이용하여 결정학적으로 확인하 였고 Fo > 4σ(Fo)를 사용하여 최종 오차 인자를 각각 R1/wR2 = 0.040/0.121 그리고 0.052/0.168로 정 밀화하였다. Crystal 1(|Cd36H3|[Si117Al75O384]-FAU)에서 Cd2+이온은 주로 site I과 site IIa에 점유되어 있었고, 이와 더불어 site I’, II’ 그리고 site IIb에도 Cd2+ 이온이 점유되어졌다. Crystal 2(|Cd35(C6H6)24H5|[Si117Al75O384]-FAU)에서 Cd2+ 이온은 다섯 개의 결정학적 자리에 점유되었다. 24개 의 벤젠분자는 supercage 내부에서 두 개의 뚜렷한 자리에서 발견 되었다. 17개의 벤젠분자는 site IIa 에 있는 Cd2+ 이온과 면상에서 서로 상호작용하였고 supercage 안에서 3회 회전축 상에서 발견되었다. 나머지 7개의 벤젠분자는 12-ring 면상에서 골격(framework)산소들과 함께 약한 다수의 정전기적인 작용과 van der Waals 상호작용으로 안정화되어 있었다.

The aim of this study was to examine the morphological responses of Hosta longipes, an ornamental plants for heavy metal contaminated soils in urban landscaping, to heavy metals Cd, Pb, and Zn. Plants were grown in artificial soil amended with Cd, Pb, and Zn at concentation of 0, 100, 250, and 500 mg/kg. Plant height, leaf length, leaf width, total leaf number, deaf leaf number, new leaf number, chlorophyll contents, and ornamental value were monitored from May to August. At 4 months after planting, the survival and morphological responses of H. longipes grown in soil amended with Cd at concentrations ≥ 100 mg/kg were severely affected compared to those grown in the control soil. Relative leaf length rate and relative leaf width rate were significantly decreased when the concentration of Pb was increased. Total leaf number, chlorophyll contents, and ornamental value were the lowest value in plants grown in soil amended with Pb at level of 500 mg/kg. Relative leaf length rate and relative leaf width rate, total leaf number, dead leaf number, new leaf number, and ornamental values had a tendency of decrease when plants were grown in soils amended with Zn. However, no significant difference was found among treatments except for plants were grown in soils amended with 500 mg/kg Zn. Therefore, Hosta longipes might be useful for phytoremediation of Zn contaminated sites as herbaceous ornamental plants.

This study attempted to facilitate various groundcover plants, related to phytoremediation material, and advance shade plants with a heavy metal tolerance to contaminated soil in an urban shade space. Saxifraga stolonifera, which has commonly been used a landscape shade plants, was evaluated to determine its heavy metal tolerance to different concentrations(Control, 100mg․kg-1, 250mg․kg-1and 500mg․kg-1 treatment) of Cd, Pb and Zn in soil. The growth of Saxifraga stolonifera showed no significant tendency after the initial transplantation, but showed distinct changes with the respective treatment heavy metal types and concentrations over time. Especially, severe chlorosis, with more yellowish green leaves, was observed, with inhibition at Cd concentrations greater than 100mg․kg-1. Conversely, no external symptoms or growth retardation were observed with Pb and Zn concentrations less than 500mg․kg-1. Therefore, Saxifraga stolonifera can be applied as a long term phytoremediation species in soil contaminated with low concentrations of heavy metal in urban shade spaces.

본 연구는 화단국을 이용하여 미적 가치를 제공할 수 있는 관상식물의 중금속에 대한 생육 양상 및 중금속 축적 능력을 확인함으로써 오염지의 경광조성 및 환경친화적인 중금속 정화방법인 식물복원법(phytoremediation)의 가능성을 규명을 위해 화단국인 도입품종인 ‘Branivory'과 국내 육성 품종인 ‘금방울’과 ‘화이트 미리’를 공시하여 토양 내에 Cd를 처리하여 생육량과 생리적 특성을 조사하였다. 공시 3품종의 신초장은 Cd처리구에 비해 대조구에서 다소 높았고, 특히 화이트 미리’는 216mm의 가장 높은 신초장을 보였고, Cd 처리구에서는 대조 품종인 ‘Branivory'에 비해 국내 육성종인 ‘화이트 미리’는 처리구의 16주에서 높은 196mm의 신초장을 보였다. 지상부 생체중과 건물중에서도 ‘화이트 미리’는 대조구에 비해 낮은 것으로 보였으나, 다른 품종에 비해 16주의 Cd 처리구에서는 높은 23.7g의 생육반응을 나타내는 특성을 보였다. 또한 식물체 내의 생리물질의 변화에 있어서는 수용성 단백질 함량은 Cd 처리구에서는 전체적으로 대조구에서 그 함량이 증가하였으나, 수용성 탄수화물에서는 시간별 품종간 차이를 보였는데 ‘Branivory’와 ‘금방울’에서는 8주차에서 가장 높은 경향을 보였다. 엽록소 함량은‘금방울’ 품종에 있어서는 8주 대조구에서 4.81mg/g으로 가장 현저하였다. 한편 Cd 처리구에서 생육량과 생리적 양상에서 다소 저해를 보였지만 축적량이 증가하는 경향을 보였고, '금방울’에서 8주의 2.88ppm, 16주의 7.04ppm 이었고, ‘Branivory'는 1.55ppm(8주), 2.56ppm(16주)으로, ‘화이트 미리’에서는 0.31ppm(8주), 0.88ppm(16주) 순으로 품종간 차이가 현저하였다. 따라서 국내 육성품종과 도입품종의 간의 비교에서 토양오염지에서 국내 육성품종에 있어 생육상에서는 화이트 미리’가 우수한 생육반응을, 중금속 축적에서는 '금방울’에서 우수함을 나타냄으로써 경관조성이 가능한 phytoremediator로서의 가능성이 있을 것이라 생각된다. 그러나 또한 그 효과를 극대화시키기 위해 보다 많은 품종의 비교실험이 필요할 것으로 생각되며, 인산, 소석회, 토양개량제 등의 첨가를 통한 토양내 bioavailability를 높이고 활착과 보다 많은 건물생산량을 높일 수 있는 연구가 뒤따라야 할 것으로 생각된다.

Cd contamination in irrigation water can imperil human health through food chain. In order to investigate the genotypic differences in Cd accumulation of rice, thirty-five rice cultivars of different cultivar groups (temperate japonica, tropical japonica, tongil, and indica) were grown with irrigation water containing 2 ppm Cd throughout all growing season under the field condition in 2007. At harvest, highly significant differences in Cd concentration in different rice parts (root, shoot, straw, grain, chaff, brown rice, rice bran, and polished rice) was found among rice varieties and rice cultivar groups. Cd concentration of polished rice ranged from 0.26 to 1.85 mg/kg. The total Cd accumulation of shoot varied from 0.69 to 7.87 mg/m2. Indica cultivar group showed significantly higher Cd concentration and accumulation compared to the other rice cultivar groups. On the other hand, the distribution ratio in polished rice was the highest in Tongil cultivar group. The large genotypic variation suggested the possibility of breeding low Cd accumulating rice variety.

AtHMA3 is one of P1B-ATPase of Arabidopsis thaliana which transports and/or stores Cd and Pb in the plant cell. To test whether AtHMA3 can be used to develop enhanced resistance plant to Cd and Pb for phytoremediation, we overexpressed AtHMA3 in Columbia-0 using a pBI121vector containing the 35S promoter. To evaluate their Cd and Pb resistance, seeds of three different T3 homozygous(HMA3-1~3) and wild type plants(col-0) were germinated and grown on agar plates containing 50μM Cd, 500μM Pb and 50μM Cd+ 500μM Pb for 3 weeks. 35S::AtHMA3 grew better than wild type plants about 1.1-to 1.8-fold in Cd or Pb containg mediums. Fresh weights of all three lines of transgenic plants were 1.2-to 1.5-fold higher than those of wild type plants in Cd or Pb-containing medium. In addition to, we measured Cd and Pb content in both wild type and transgenic plants grown in solution with 50μM Cd, 500μM Pb and 50μM Cd+ 500μM Pb for 6 d. AtHMA3-overexpressing plants had consistently higher Cd and Pb contents than wild type plants. Chlorophyll contents were not significant difference between overlines and wild-types. These results show that HMA3 contributes to Cd and Pb resistance, and it might be useful for the phytoremediation.

Effects of salinity and standard toxic metals on fertilization and embryo development rates were investigated in the sea urchin, Strongylocentrotus nudus. Spawning was induced by injecting 1㎖ of 0.5 M KCl into the coelomic cavity. The fertilization and embryo development rates were below 20% when salinity was 25 psu or lower, but were above 90% when salinity was between 30 and 35 psu. The fertilization and embryo development rates in the control condition (not including Cu and Cd) were greater than 90%, but decreased with a high negative correlation (r) of 0.89 and 0.91 with the increasing of Cu and Cd concentrations, respectively. These results suggest that salinity concentrations for successful fertilization and normal embryogenesis of S. nudus are between 30 and 35 psu, and the biological assays of fertilization and embryo development rates using S. nudus are useful methods for the ecological toxicity test of marine pollution elements.

둥굴레 근경의 증자 및 열처리 중 수용성 고형분 및 Pb, Cd 제거율의 변화를 확인하기 위하여 반응표면분석(RSM)을 활용하였다. 중심합성계획법에 따라 증자시간( min), 볶음온도() 및 볶음시간( min)을 달리하여 16구간으로 제조된 시료의 수용성 고형분 함량, Pb 및 Cd 제거율을 측정하고 회귀분석을 실시하였다. 예측된 가용성 고형분의 최대값은 이었으며, 이때의 증자 및 볶음조건은 증자시간 65.24분, 볶음온도 및 볶음시간 37

Three-week old Commelina communis was transferred and grown in Hoagland solution containing 100μM Cd2+, 100μM Cd2++100μM kinetin, 100μM Cd2++100μM zeatin and 100μM Cd2++200μM zeatin for 7 days, and then a number of physiological activities were investigated. In control, the length of the stem of plants was increased to 4.7cm, but in Cd2+, Cd2++kinetin, Cd2++100μM zeatin and Cd2++200μM zeatin treatments, the growth of plants were increased to 1.5cm, 2.1cm, 3.9cm and 4.3cm, respectively. In the treatments of Cd2+, Cd2+ +kinetin, Cd2++100μM zeatin and Cd2++200μM zeatin, total chlorophyll contents were reduced to 26%, 24%, 15% and 3%, respectively, on the contrast to the control. In chlorophyll fluorescence experiments, Fv/Fm ratios were also reduced to 44%, 21%, 17% and 5% in the light intensity of 2100μmole E m-2s-1 by Cd2+, Cd2++ kinetin, Cd2++100μM zeatin and Cd2++200μM zeatin treatments on the contrast to the control. Water stresses were increased to 2.6, 1.7 and 1.2 times by Cd2+, Cd2++kinetin and Cd2++100μM zeatin. On the other hand, combination of Cd2++200μM zeatin reduced water stress to 0.12%. In Cd2+ accumulation experiments Cd2+ transports were inhibited to 33%, 48% and 70% by Cd2++kinetin, Cd2++100μM zeatin and Cd2++200μM zeatin. Therefore, it could be concluded that zeatin clearly reduced the toxicities of Cd2+ by reducing the absorption of Cd2+.

3-weeks old Commelina was transferred to and grown in Hoagland solution (Control, 100μM Cd2+, 100μM Cd2++100μM IAA, 100μM Cd2++100μM IAA+2 mM sucrose) for 3 weeks and then the effects of indole acetic acid (IAA) on the accumulation of Cd2+ and growth of Cd2+-treated Commelina were investigated. In the treatment of Cd2+, Cd2+ was uptaked to 1.74, and 51.36 μg/g frwt. at the first week, but for three weeks, 0.51 and 34.53 μg/g frwt. in leaf and stem respectively. When IAA was treated along with Cd2+, Cd2+ was uptaked to 0.18 and 8.63 μg/g frwt. at the first week, and for the incubation of 3 weeks, 0.51 and 45.0 μg/g frwt. in leaf and stem. In case of Cd2++IAA+sucrose, Cd2+ was uptaked to 1.45 and 18.33 μg/g frwt. at the first week, but for 3 weeks, 0.51 and 25.45 μg/g frwt. in leaf and stem. Likewise Cd2+ uptake, the growth was also affected by Cd2+ and IAA. During the incubation of 3 weeks, Cd2+ reduced the stem growth about 8% in all weeks, but the treatment of IAA recovered the inhibition of stem growth caused by Cd2+ to the degree of the control Therefore, it could be concluded that IAA altered the pattern of Cd2+ uptake and the growth which were supposed to change Cd2+ toxicity.

The thiophene or furan-containing hexadentate ligands 1,12-bis (2-theophene)-2,5,8,11-tetraazadodecane(Thiotrien ․4HCl) and 1,12-bis (2-furan)-2,5,8,11-tetraazadodecane(Furatrien․4HCl) were synthesized as their tetrahydrochloride salt and characterized by EA, IR, NMR, and Mass spectrum. Their protonation constants (logKnH) and stability constants (logKML) for Cd2+, Pb2+, Zn2+ and Cu2+ ions were determined in aqueous solution by potentiometry and compared with 1,12-bis(2-pyridyl)-2,5,8,11-tetra-azadodecane(Pytrien) of pyridyl-containing ligand. The effect stability constants of ligands and metal ion for removal of heavy metals in aqueous solution were described.

Three kinds of toxic heavy metals, such as lead, copper, and cadmium, existing abundantly in contaminated soils were selected to investigate pH change, electroosmotic flow, and the removal rate in the application of electrokinetic process. In the change of pHs, they reached to about 12 and 2 at each cathodic and anodic region, respectively, and maintained for reaction being proceeded. Electroosmotic flow rates were not influenced by the kind of metal species but by electropotential gradient. On the soils contaminated by each metal, the removal rate of Cd was the fastest among three as in the order of Cd>Pb>Cu. While on the soils contaminated by mixed metal species, Cu was the fastest. Metal species transported by electrokinetic processes were distributed in between 0.9 and 1.0 of normalized region. In the case of soils contaminated by one kind of metal. the relative concentrations of Pb and Cd estimated in between normalized region 0.9 and 1.0 were 5.2 and 5.7, respectively.

Various kinds of zeolites, such as analcime (ANA), cancrinite (CAN), Na-P1 and sodalite octahydrate (SOD) could be synthesized from Hwangto by hydrothermal reaction in a high-pressure vessel. The adsorption characteristics of Cu(II) and Cd(II) by Hwangto and its synthetic zeolites were investigated using the chemical and electrochemical surface parameters of these adsorbents. The heavy metal adsorptivity among the adsorbents decreased in the following sequences: Na-P1>SOD>ANA>CAN>Hwangto. This sequence was the same with the values of surface site density (Ns) of these adsorbents and was correlated inversely with the values of pHpzc (pH of the point of zero charge) and the values of Ka2(int) (intrinsic surface deprotonation constant) of the adsorbents for synthetic zeolites, i.e., the adsorbents with higher values of Ns and with lower values of pHpzc and Ka2(int) for synthetic zeolites showed higher heavy metal adsorptivity. With increasing pH, the heavy metal adsorptivity increased greatly between pHpzc and pH 6 or 7 because of the steep increase of negatively charged sites for synthetic zeolites, but for Hwangto, it increased broadly because of slow increase of negatively charged sites based on its lower surface sites.

The new tridentate ligands of nitrogen doner atoms N,N-Bis(2-amino-ethyl)-benzyl-amine·2HCl(BABEA·2HCl) and 2,6-Bis(amino-methyl)-pyridien·2HCl(BAMP·2HCl) were synthesized as their dihydrochloride salts and characterized by EA, IR, Mass and NMR spectroscopy. The protonation constants of the ligands and stability constants for Cd2+, Pb2+, Zn2+and Cu2+ ions were determined by potentiometric titration in aqueous solutions and compared with those of analogous ligands. The effect stability constants of ligands and metal ions for removal of heavy metals in aqueous solution were described.

The growth and heavy metal experiments revealed oppositive interactions between toxic metals(Zn and Cd) and Mn when the coastal diatom T. pseudonana were used. Cd and Zn inhibited the algal growth rate only at low Mn ion concentrations and this effect could be accounted for an inhibition of cellular Mn take by the toxic metals. Mn and Zn inhibited cellular Cd take and this indicated a reciprocal effects among the metals with respect to metal take. Saturation kinetics modeling of the take data was consistent with two metals competing with each other for binding to the Mn take system and with both Cd and Mn being transported into the cell by that system. Mathematical modeling of Mn and Cd take data revealed evidence for a Cd efflux system.

방해석 표면에 의한 Cd2+의 흡착연구를 하였다. 흡착실험에서 사용한 Cd의 농도는 10-8 로서 CdCO3(s)의 침전농도 보다 낮은 농도를 유지하도록 조절하였다. NaClO4를 전해질로 사용하여 이온농도를 달리 한 실험 결과 Cd2+의 흡착은 용액의 이온세기와는 무관한 것으로 나타났다. 이는 Cd2+의 방해석 표면 흡착이 특징적인 성질을 갖고 inner sphere surface complex를 형성한다는 것을 암시한다. 흡착반응은 초기의 매우 빠른 흡착시기와 후기의 지속적인 느린 흡착시기의 2단계로 구분되었다. 특히, 후기의 느린 흡착시기에는 약 145시간 경과 후 최대정상상태 (steady state maximum)에 도달하였다. 본 연구에서 사용한 Cd2+의 농도가 낮아 방해석 표면에 CdCO3(s)의 침전 형성에 의한 반응은 고려되지 않았다. 방해석 표면으로부터 Cd2+의 탈착반응은 일정시간의 흡착 반응이 경과된 후 초기 흡착 실험 시와 같은 농도의 과포화 용액을 사용하여 Cd2+을 흡착한 방해석이 새로운 용액에 재 평형을 이루도록 반응을 유도하였다. 일반적으로 탈착실험에서는 새로운 과포화용액에 방해석을 넣자마자 매우 빠른 탈착반응을 보여준다. 그 이후는 2가지의 다른 경향성을 보여주며 새로운 평형에 도달하는 것으로 나타난다. 초기의 빠른 탈착반응 시기 뒤 느린 흡착반응이 지속적으로 일어나 일정 시간 경과 후 다시 평형을 이루거나, 느린 탈착반응이 계속적으로 지속되어 일정 시간 경과 후 새로운 평형을 이루는 2가지로 나타났다. 이러한 부분적으로 비가역적인 흡착 반응과 탈착반응은 실제 자연계에서 Cd2+의 유동성을 결정짓는 매우 중요한 인자로 작용할 것으로 생각된다. 흡착 반응 및 탈착반응의 평형상수 값은 이들 반응이 서로 동일한 기작에 의하여 조절됨을 보여주었다.