Heavy metal ions pollution has become of worldwide critical concern, thus, it is particularly important to monitor it in the environment and food for ensuring human health. In this study, p-phenylenediamine and 2-mercaptothiazoline were used to prepare nitrogen (N) and sulfur (S) co-doped carbon dots (N/SCDs) for fluorescent and colorimetric detection of Cu2+. The fabricated N/SCDs with bright green fluorescence showed excellent optical characteristics and favorable water solubility. In an aqueous system, a significant fluorescence quenching of N/SCDs at 512 nm is obtained in the presence of Cu2+. It also caused a significant colorimetric response with the color of prepared N/SCDs solution changed from colorless to yellow. Under optimal conditions, the analytical results showed that the linear range spanning from 5 to 400 μM, with a detection limit of 0.215 μM in fluorescence and 0.225 μM in colorimetric detection. In addition, N/SCDs displayed high selectivity toward Cu2+. No obvious interference was observed over other metal ions. Furthermore, we have also used N/SCDs to monitor Cu2+ in tap and lake water. The recovery of Cu2+ ranged between 89.6% and 113.1%. Exhibiting remarkable sensitivity and selectivity, the designed sensor offers a promising detection method for Cu2+ detection in the real sample.

Heavy metal wastewater containing cobalt (Co2+) has received more attention as an environment issue, which is released from electroplating processes, battery materials industries, nuclear power plants, etc. Especially, cobalt exposed to high-temperature and high-pressure environment during the operation of a nuclear power plant to form corrosion products and forming a chalk river unidentified deposit (CURD) along with radioactive materials generated in cooling water pipes. Cobalt present in the oxide film is mainly Co-60, which emits radiation and causes increased radiation exposure to workers, and efficient management is essential. In this study, we demonstrated the performance of copper hexacyanoferrate (CuHCF) electrodes in a capacitive deionization (CDI) system for Co2+ ions removal. The structure and chemical status of CuHCF used as an electrode material were characterized, and electrochemical properties were evaluated. This study showed that Co2+ ions could be efficiently removed in aqueous solutions using CuHCF electrodes. It has been experimentally shown that the ion removal mechanism is driven by the insertion of Co2+ ions within the CuHCF lattice channels. The deionization capacities in 20 and 50 mg-Co2+ L-1 aqueous solutions were 141.62 and 156.85 mg g-1, respectively, and the corresponding charge efficiencies (Λ) were 0.55 and 0.68, respectively. Thus, we suggest that an electrochemically driven process using CuHCF can usefully remove Co2+ ions from wastewater.

This study used a packed column reactor and a horizontal flow mesh reactor to examine the removal of copper ions from aqueous solutions using pine bark, a natural adsorbent prepared from Korean red pine (Pinus densiflora). Both equilibrium and nonequilibrium adsorption experiments were conducted on copper ion concentrations of 10mg/L, and the removals of copper ions at equilibrium were close to 95%. Adsorption of copper ions could be well described by both the Langmuir and Freundlich adsorption isotherms. The bark was treated with nitric acid to enhance efficiency of copper removal, and sorption capacity was improved by about 48% at equilibrium; mechanisms such as ion exchange and chelation may have been involved in the sorption process. A pseudo second-order kinetic model described the kinetic behavior of the copper ion adsorption onto the bark. Regeneration with nitric acid resulted in extended use of spent bark in the packed column. The horizontal flow mesh reactor allowed approximately 80% removal efficiency, demonstrating its operational flexibility and the potential for its practical use as a bark filter reactor.

탄소전극과 이온교환막을 결합한 축전식 탈염(CDI)을 이용하여 셀 구조와 셀 전위에 따른 구리 이온의 제거 특성을 연구하였다. 탄소전극과 이온교환막의 결 합 방식에 따라 4종류의 셀에 대해 실험한 결과 양이온, 음이온교환막을 결합한 셀(MCDI)에서 구리 이온의 제거율과 전하효율이 가장 높은 것으로 나타났다. 셀 전위에 따른 영향을 분석한 결과 0.6 V 이하에서는 전기이중층에 의한 전기 흡착(electrosoprtion)에 의해, 그리고 0.6 V 이상에서는 구리 이온의 전착 (electrodepostion)반응에 의해 구리 이온이 제거됨을 확인하였다. 또한 1.2 V 이상에서는 물이 전기분해되어 전하효율이 감소하였다. MCDI 셀의 운전결과 전하효율은 80% 정도로 구리 이온을 포함한 중금속 이온을 제거하는데 효과적인 것으로 판단되었다.

탄소전극과 이온교환막을 결합한 막결합 축전식 탈염(MCDI) 셀을 이용하여 환원전위가 다른 Na+과 Cu2+ 이온 혼합용액에서 Cu2+ 이온의 제거 특성을 연구 하였다. MCDI 셀에 일정한 전류밀도(1.5 mA/cm2)를 공급하면서 탈염을 실시한 결과 Cu2+ 이온은 일정한 제거속도를 유지하였지만 Na+ 이온의 제거량은 시간에 따라 감소하였다. 이는 Cu2+ 이온은 전착반응에 의해, Na+ 이온은 전기흡착 반응에 의해 제거되기 때문인 것으로 판단된다. Cu2+ 이온의 당량비가 0.14, 0.38, 0.50인 혼합용액을 탈염한 결과 제거된 이온 중 Cu2+ 이온의 당량비는 각 각 0.27, 0.60, 0.79로 나타났다. 이를 통해 Cu2+ 이온의 전착반응에 의해 혼합용 액에서 Cu2+ 이온의 제거율을 증가시킬 수 있음을 알 수 있었다.

PVA-D2EHPA/TOPO beads containing two extractants, di-(2-ethylhexyl) phosphoric acid (D2EHPA) and trioctylphoshine oxide (TOPO) were prepared for the removal of copper ions from aqueous solution. The prepared PVA-D2EHPA/TOPO beads were characterized by SEM and FT-IR. The removal characteristics of copper ions by PVA-D2EHPA/TOPO beads was investigated using batch and continuous systems. In batch experiments, the maximum removal capacity calculated from Langmuir isotherm model was 18.6 mg/g and the optimal pH was in the range of 4.5 ∼6. The continuous experiments showed that the removal capacity of copper ions increased with increasing inlet copper ion concentrations and bed heights, but decreased with increasing inlet flow rates.

Adsorption on goethite of individual component from a solution containing phosphate, sulfate, or copper ion was investigated. Competitive adsorption in the binary and ternary solution systems composed of phosphate, sulfate, and copper ions was also investigated. In competitive adsorption systems with phosphate and sulfate ions, the presence of phosphate ion reduced the adsorption of sulfate ion largely. On the other hand, the presence of sulfate ion caused only a small decrease in phosphate adsorption. This result suggests that phosphate ion is a stronger competitor for adsorption on goethite than sulfate ion, which is consistent with the higher affinity of phosphate for the surface compared to sulfate ion. Compared to the results from single-sorbate systems, adsorption of copper ion in the binary system of sulfate ion and copper ion was found to be enhanced in the presence of sulfate ion. Addition of sulfate ion to the binary system of copper ion and phosphate ion resulted in a small enhancement in copper sorption. This result implies that the presence of sulfate ion promotes adsorption of the ternary complex FeOHCuSO4. The adsorption isotherms could be well described by the Langmuir adsorption equation.

Adsorption of phosphate, sulfate, and copper ion to goethite was investigated. Goethite was prepared in the alkaline solution. In the single adsorbate systems, the final equilibrium plateau reached within 20 min. The adsorption isotherms of the individual ions could be well described by the Langmuir equation. The maximum adsorption capacities (qmax) were calculated as 0.483 mmol/g and 0.239 mmol/g at pH 3 for phosphate and sulfate ion, and 0.117 mmol/g at pH 6 for copper ion, respectively. In competitive adsorption system with phosphate and sulfate, phosphate ion was a stronger competitor for adsorption on goethite than sulfate ion, which was consistent with higher affinity of phosphate ion for the surface compared to sulfate ion. The existence of sulfate ion enhanced the adsorption of copper ion but the adsorption of sulfate was inhibited when copper ion was present.

To find heavy metal-specific effects on the photosynthetic apparatus of higher plants, we investigated effects of CuCl_2, HgCl_2 and ZnCl_2 on electron transport activity and chlorophyll fluorescence induction kinetics of chloroplasts isolated from barley seedlings. Effects on some related processes such as germination, growth and photosynthetic pigments of the test plants were also studied. Germination and growth rate were inhibited in a concentration-dependent manner by these metals. Mercury was shown to be the most potent inhibitor of germination, growth and biosynthesis of photosynthetic pigments of barley plants. In the inhibition of electron transport activity, quantum yield of PSⅡ, and chlorophyll fluorescence induction kinetics of chloroplasts isolated from barley seedlings, mercury chloride showed more pronounced effects than other two metals. Contrary to the effects of other two metals, mercury chloride increased variable fluorescence significantly and abolished qE in the fluorescence induction kinetics from broken chloroplasts of barley seedlings. This increase in variable fluorescence is due to the inhibition of the electron transport chain after PSⅡ and the following dark reactions. The inhibition of qE could be attributed to the interruption of pH formation and de-epoxidation o1 violaxathin to zeaxanthin to thylakoids by mercury. This unique effect of mercury on chlorophyll fluorescence induction pattern could be used as a good indicator for testing the presence and/or the concentration of mercury in the samples contaminated with heavy metals