Removal of Ni(II) and Cu(II) from aqueous solutions using 'green' zero-valent iron nanoparticles produced by oak and mulberry leaf extracts.

The production of zero-valent iron nanoparticles, using extracts from natural products, represents a green and environmentally friendly method. Synthesis of 'green' zero-valent nanoparticles (nZVI) using oak and mulberry leaf extracts (OL-nZVI and ML-nZVI) proved to be a promising approach for Ni(II) and Cu(II) removal from aqueous solutions. Characterization of the produced green nZVI materials had been conducted previously and confirmed the formation of nanosize zero-valent iron particles within the size range of 10-30 nm, spherical with minimum agglomeration observed by transmission electron microscopy and scanning electron microscope morphology measurements. Batch experiments revealed that the adsorption kinetics followed a pseudo-second-order rate equation. The obtained adsorption isotherm data could be well described by the Freundlich model and OL-nZVI showed higher adsorption capacity for Ni(II) removal than ML-nZVI, while ML-nZVI adsorption capacity was higher for Cu(II). In addition, investigation of the pH effect showed that varying the initial pH value had a great effect on Ni(II) and Cu(II) removal. Adsorbed amounts of Ni(II) and Cu(II) increased with pH increase to pH 7.0 and 8.0. This study indicated that nZVI produced by a low-cost and non-toxic method with oak and mulberry leaf extracts could be used as a new material for remediation of water matrices contaminated with Ni(II) and Cu(II).

A comparison of sediment quality results with acid volatile sulfide (AVS) and simultaneously extracted metals (SEM) ratio in Vojvodina (Serbia) sediments.

The acid-volatile sulfide (AVS), simultaneously extracted metals (SEM), total metals, and pore-water metal concentrations were studied in Vojvodina (Serbia) sediments. In Serbia, there are no regulations concerning sediment quality standards and sediment management. Harmonization of legislation in the domain of environmental protection with EU requirements will increase the significance of the sediment issue. Sediment quality was assessed according to Dutch standards, but the results were also compared with Canadian and USEPA (United States Environmental Protection Agency) guidelines for sediment quality. A comparison of the results based on different criteria for sediment quality assessment shows that they are sometimes contradictory. Therefore, a single approach to quality assessment may be insufficient. The Sigma[SEM]/[AVS] ratio was found to be greater than one at several locations that were already recognized as places of high risk based on Dutch standards. Some other samples had Sigma[SEM]/[AVS]<1, despite of the high risk classification based on the Dutch evaluation. However, not all sediments with Sigma[SEM]/[AVS]>1 can cause increased toxicity because there are many other metal-binding phases in sediments. Metals that are associated with AVS may be released within sediments through storms, dredging activities, oxidation, etc., and may have adverse environmental impacts. This has to be taken into account during dredging, which is for some sediments necessary because the sediment is of class 4 (Dutch evaluation), because the dredging process will certainly increase the concentration of bioavailable heavy metals and disturb the sedimentation dynamics. The obtained results will be invaluable for future activities regarding dredging and sediment management in the country.

Pollution of the Begej Canal sediment--metals, radioactivity and toxicity assessment.

The Begej Canal is one among a large number of canals in Vojvodina (Northern Province of Serbia and Montenegro). The paper describes a study of metal and radioactivity contamination of the Begej Canal sediment. It is also concerned with the evaluation of sediment acute toxicity based on standard test species Daphnia magna and simultaneously extracted metals and acid volatile sulfides. The quality of sediment was assessed according to Dutch standards, but the results were also compared with some Canadian and USEPA (United States Environmental Protection Agency) guidelines for sediment quality. The results showed severe pollution with chromium, copper, cadmium and zinc, whereby the anthropogenic origin of these contaminants was indicated. The tests of toxicity of sediment pore water to D. magna, gave no indication of the presence of substances in acutely toxic concentrations to this species. It can be speculated that, despite of high metal contents, the observed toxicity was low because of the high contents of clay and iron, as well as sulphide. Also, based on a comparison with the Danube sediment and Vojvodina soil in general, the data of the Begej sediment contamination with 238U and 137Cs. The 137Cs data were used for approximate dating of the sediment. No traces of contamination by nuclear power plants in the region were found, while the presence of technologically enhanced naturally occurring radioactive materials (TENORM) was proved. Conclusions based on different criteria for sediment quality assessment were in some cases contradictory. Study also showed that radioactivity aspects can be useful in sediment quality surveys. The obtained results will be invaluable for the future activities regarding integrated water management based on EC Water Framework Directive (2000/60/EC) in the Danube basin, and particularly in the region of crossborder water body of the Begej Canal.

Kinetics of degradation of hydrocarbons in the contaminated soil layer.

This work presents kinetic parameters of the removal of hydrocarbons in the course of bioremediation of the soil contaminated with crude and oil derivatives, with special emphasis paid to polycyclic aromatic hydrocarbons. Bioremediation was carried out on a laboratory scale, with continuous and discontinuous recirculation of water through the soil column inoculated with the adapted bacterial population. Biodegradation of hydrocarbons can be described by the following equation--ln C = ln C0- kt--which is most often used in the literature to describe degradation of hydrocarbons, and by the equation--ln C = ln C0- kt0.5--which is determined on the basis of experimental data (except for pyrene and chrysene, for which a linear equation was used). A comparison of the two models showed a significant difference in the calculated remediation times, indicating that it is not realistic to expect a simple kinetic model to provide precise and accurate descriptions of concentrations during different seasons and in different environments. The results indicated that once contaminated with hydrocarbons, soil can be slowly brought to the previous state provided that no new contamination has occurred.

Croatia has reached iodine sufficiency.

This study was performed in 2002, 6 yr after the introduction of a new regulation on salt iodination with 25 mg KI/kg of salt. The aim of the study was to evaluate whether further significant positive results of improved iodine intake could be observed among schoolchildren in Croatia. A total of 927 schoolchildren of both sexes, aged 6-12 yr, were included in the study. In Croatia, with a population of 4,437,460 the research was implemented in four major geographical regions: the Northwestern, Slavonia, Northern Adriatic and Dalmatian regions. Investigations included randomly selected pupils from regional centers and neighboring smaller towns or villages. The results have revealed that thyroid volumes were within the normal range according to the provisional WHO/ICCIDD reference values for sonographic thyroid volume in iodine-replete school-age children, updated in 2001. A significant improvement in medians of urinary iodine excretion was detected in 2002: from 9 microg/dl in 1991 to 14.6 microg/dl in Zagreb, from 4.3 microg/dl in 1995 to 13.1 microg/dl in Split, from 9.4 microg/dl in 1997 to 14.2 microg/dl in Rijeka and from 13.4 microg/dl in 1997 to 14.7 microg/dl in Osijek. An overall median of 14.0 microg/dl of urinary iodine excretion was detected in Croatian schoolchildren. The control of salt at different levels, from production to consumption, including salt produced in all three Croatian salt plants and imported salt, revealed that Croatian salt is adequately iodized. From severe iodine deficiency before the 1950s, through mild-to-moderate iodine deficiency in the 1990s, Croatia has now reached iodine sufficiency.

[Endemic goiter in Croatia]. / Endemska gusavost u Hrvatskoj.

In the early nineties, 40 years after the introduction of iodine prophylaxis in Croatia (10 mg KI/kg salt), a nationwide study was initiated with the aim to determine the real prevalence of goiter in the country. A total of 2436 schoolchildren of both sexes, aged 7-15 years, were included in the study. Investigations were designed in a way to cover most of geographical regions in Croatia and subjects were randomly selected. The prevalence of goiter in schoolchildren was assessed by palpation and in part by ultrasonography of the neck. At the same time urinary iodine excretion was measured and potassium iodide content in salt samples was determined. The results revealed the persistence of mild endemic goiter in the inland parts of Croatia with the prevalence of 6-29% in the age group 7-11 years and 10-43% among the age group 12-15 years. The overall goiter prevalence in schoolchildren in Croatia fluctuates from 8% to 35%. The urinary iodine excretion in Zagreb varied from 1.6 to 24.4 micrograms/dL with a median of 9.0, while in 14% it was below 5 micrograms/dL. The urinary iodine excretion in Samobor varied between 0.5 and 19 micrograms/dL with a median of 7.4 micrograms/dL, while in 30% it was below 5 micrograms/dL. Examination of salt from all three salt plants in Croatia showed iodine contents between 0.0 and 12.73 mg/kg with the average value of 5.39 mg/kg. Such prevalence, most probably due to less than optimum iodine intake, is unlikely to change until potassium iodide content of salt is increased from its present level of 10 mg of KI per kg of salt, with concomitant stricter observance of legal regulations.

Current status of endemic goiter in Croatia: the results of a nationwide study (1995).

In the beginning of the nineties, 40 years after introduction of iodine prophylaxis in Croatia, on a basis of a frequent reports coming from general practitioners about the presence of a rather high prevalence of goiter among schoolchildren, a nationwide study was initiated with the aim to determine the real prevalence of goiter in the country. A total of 2856 schoolchildren of both sexes, aged 7-15 years, were included into the study. Investigations were designed in a way to cover most of geographical regions in Croatia and subjects were randomly selected. The prevalence of goiter in schoolchildren was assessed by palpation and in part by ultrasonography of the neck. At the same time urinary iodine excretion was measured and iodine content in salt samples was determined. The results have revealed the persistence of mild endemic goiter in inland parts of Croatia with the prevalence of 6-29% in the age group 7-11 years and those of 10-43% among the age group 12-15 years. The overall goiter prevalence in schoolchildren in Croatia fluctuates from 8% to 35%. Such prevalence, most probably due to less than optimum iodine intake, is unlikely to change until iodine content of the salt is increased from its present level of 10 mg of Kl per kg of salt.

Thyroglobulin determination, neck ultrasonography and iodine-131 whole-body scintigraphy in differentiated thyroid carcinoma.

UNLABELLED: The long-term prognosis of patients with differentiated thyroid carcinoma depends on the early diagnosis and treatment of metastases and local recurrences. We evaluated serum thyroglobulin measurements, neck ultrasonography with ultrasound-guided biopsy and 131I whole-body scintigraphy in the follow-up of 359 patients after surgical thyroidectomy and radioiodine ablation of the thyroid remnant. METHODS: Serum thyroglobulin levels were determined and considered abnormal when the values were > 5 ng/ml. Ultrasonography over the entire neck region and fine-needle aspiration biopsy of the mass or enlarged lymph nodes were carried out using 5- and 7.5-MHz transducers and 23-gauge needles. Whole-body scintigraphy was performed after administration of 185 MBq (5 mCi)131I. RESULTS: Increased levels of thyroglobulin (ranging from 12 to > 600 ng/ml) were measured in 40 of 55 (73%) patients with metastases or local recurrences. Ultrasonography revealed occult neck masses that were not detected by other methods. Neck ultrasonography and ultrasound-guided biopsy were positive for malignancy in 23 patients. Thyroglobulin levels were undetectable in 12 (52%) of these patients and 131I whole-body scintigraphy was negative in 19 (83%) of them. CONCLUSION: The combined use of three diagnostic modalities (measurement of serum thyroglobulin, neck ultrasonography with ultrasound-guided biopsy for detecting recurrences of carcinoma in the neck region and 131I whole-body scintigraphy) appears to give the best results in the follows-up patients with differentiated thyroid carcinoma.