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Abstract

Arsenic content was determined in the soil profiles collected from the former dumping ground of post-crystallization lye (presently under recultivation) in the area of the chemical plant in Luboń, near Poznań. Of particular concern was the content of the two most toxic species ofAs(lll) and As(V) in the environmentally available exchange fraction. Extraction was performed with a phosphate buffer of pH= 6.0 ± 0.2, and the analytical method applied was HPLC-HG-AAS. As(V) species were found in all samples, whereas As(III) species in a few samples collected at different depths. The concentration of As(V) varied from 91 to 1228 ng/g, while that of As(ll I) - from 17 to 48 ng/g. As there are no watertight rock formations underneath the dumping site, the polluting substances can he easily washed out by ground waters and carried into the Warta River, which is a main source of water for the city of Poznań.
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Authors and Affiliations

Lidia Kozak
Przemysław Niedzielski
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Abstract

Arsenic is an important metalloid that can cause poisoning in humans and domestic animals. Exposure to arsenic causes cell damage, increasing the production of reactive oxygen species. Chitosan is a biopolymer obtained by deacetylation of chitin with antioxidant and metal ion chelating properties. In this study, the protective effect of chitosan on arsenic-induced nephrotoxicity and oxidative damage was investigated. 32 male Wistar-albino rats were divided into 4 groups of 8 rats each as control group (C), chitosan group (CS group), arsenic group (AS group), and arsenic+chitosan group (AS+CS group). The C group was given distilled water by oral gavage, the AS group was given 100 ppm/day Na-arsenite ad libitum with drinking water, the CS group was given 200 mg/kg/day chitosan dissolved in saline by oral gavage, the AS+CS group was given 100 ppm/day Na-arsenite ad libitum with drinking water and 200 mg/kg/day chitosan dissolved in saline by oral gavage for 30 days. At the end of the 30-day experimental period, 90 mg/kg ketamine was administered intraperitoneally to all rats, and blood samples and kidney tissues were collected. Urea, uric acid, creatinine, P, Mg, K, Ca, Na, Cystatin C (CYS-C), Neutrophil Gelatinase Associated Lipocalin (NGAL) and Kidney Injury Molecule 1 (KIM-1) levels were measured in serum samples. Malondialdehyde (MDA), Glutathione (GSH), Catalase (CAT) and Superoxide dismutase (SOD) levels in the supernatant obtained from kidney tissue were analyzed by ELISA method. Compared with AS group, uric acid and creatinine levels of the AS+CS group were significantly decreased (p<0.001), urea, KIM-1, CYS-C, NGAL, and MDA levels were numerically decreased and CAT, GSH, and SOD levels were numerically increased (p>0.05). In conclusion, based on both biochemical and histopathological-immunohistochemical- immunofluorescence findings, it can be concluded that chitosan attenuates kidney injury and protects the kidney.
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Authors and Affiliations

K. İrak
1
Ö.Y. Çelik
2
M. Bolacalı
3
T. Tufan
4
S. Özcan
4
S. Yıldırım
5
İ. Bolat
5

  1. Department of Biochemistry, Faculty of Veterinary Medicine, Siirt University, Siirt, Turkey
  2. Department of Internal Medicine, Faculty of Veterinary Medicine, Siirt University, Siirt, Turkey
  3. Kırsehir Ahi Evran University, Faculty of Medicine, Department of Biostatistics and Medical Informatics, Kirsehir, Turkey
  4. Department of Animal Nutrition and Nutritional Disease, Faculty of Veterinary Medicine, Siirt University, Siirt, Turkey
  5. Department of Pathology, Faculty of Veterinary Medicine, Ataturk University, Erzurum, Turkey
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Abstract

The analysis of leaching behavior of harmful substances, such as arsenic, is one of the parameters of risk assessment resulting from the storage or economic use of coal waste. The leachability depends both on the environmental conditions of the storage area as well as on the properties of the waste material itself. There are a number of leaching tests that allow to model specific conditions or measure the specific properties of the leaching process. The conducted research aimed at comparing two methods with different application assumptions. The study of arsenic leaching from waste from the hard coal enrichment process was carried out in accordance with the Polish PN-EN 12457 standard and the US TCLP procedure. The leaching results obtained with both methods did not exceed the limit values of this parameter, defined in the Polish law. Both methods were also characterized by the good repeatability of the results. The use of an acetic acid solution (TCLP method) resulted in three times higher arsenic leaching from the examined waste compared to the use of deionized water as a leaching fluid (method PN-EN 12457). Therefore, the use of organic acid tests for mining waste intended for storage with municipal waste should be considered, as the results of the basic test based on clean water leaching may be inadequate to the actual leaching of arsenic under such environmental conditions.

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Authors and Affiliations

Dorota Makowska
Katarzyna Świątek
Faustyna Wierońska
Andrzej Strugała
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Abstract

The present study describes a method for the determination of As (III) and As (V) in copper electrolytes. The method is based on the separation of As (III) from a copper electrolyte by triple liquid-liquid extraction using a non-polar organic solvent in a medium of 10-12 mol L–1 HCl. The extract contains As (III) and the raffinate-As (V), respectively. As(III) specie can be re-extracted from the organic solvent through the water. Analyzes of the concentration of As in the re-extract and raffinate were performed by ICP-OES spectroscopic method. The average recovery of arsenic by the proposed method is about 99%. Repeatability was estimated with RSD (n = 6). Selectivity and accuracy were proven by the standard addition method. The relative error for restoring the standard addition of As (III) is about 0.3%. The speciation method analysis could be applied for determination of the arsenic species in the analytical quality control of refined copper in copper tanks in the production of copper cathodes.
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Authors and Affiliations

E. Stefanov
1
ORCID: ORCID
S. Georgieva
1
ORCID: ORCID

  1. University of Chemical Technology and Metallurgy, Department of Analytic Chemistry, 8, St. Kliment Ohridski Blvd, 1756, Sofia, Sofia, Bulgaria
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Abstract

In the mining galleries of the abandoned Au-As mine in Radzimowice, diverse groups of secondary arsenates crystallized recently. They form several characteristic assemblages. In the first of them the typical minerals are bukovskýite and melanterite. The second group of secondary arsenates includes scorodite, kaňkite, zýkaite, and pitticite. The third assemblage includes Co-Ni-Mg arsenates of the erythrite-annabergite-hörnesite series. The first assemblage crystallized in a zone with a very high activity of sulphate and arsenate ions and where the pH varies within a narrow range of 2.0–3.5. The second group of secondary arsenates formed in the acidic zone. The minerals identified here suggest pH variation within fairly wide ranges, from about 2.0 to 5.5. Contrary to the first and second mineral assemblage, the Co-Ni-Mg arsenates formed under different geochemical conditions. Their crystallization took place under weak acidic to neutral conditions.
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Authors and Affiliations

Rafał Siuda
1
Anna Januszewska
1

  1. University of Warsaw, Faculty of Geology, Żwirki i Wigury 93, 02-098 Warszawa, Poland
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Abstract

W publikacji tej opisano właściwości fizykochemiczne szlamów arsenowych pozostałych po flotacji rud arsenowych i porastające je rośliny. Miejscem badań jest Złoty Stok - kolebka światowej metalurgii arsenu (1709-1961). Stwierdzono, że w warstwie ryzosfery (O- 25 cm) jest bardzo mało N, Na, Fe i próchnicy, mało P, średnia zawartość Ca i K oraz bardzo dużo Mg. Ich odczyn jest zasadowy. Analiza roślinności wykazała, że przez ok. 40 lat na szlamach pojawiło się 67 gatunków roślin naczyniowych. Są to wyłącznie apofity, wśród których dominują hemikryptofity, rośliny światłolubne i neutralne w stosunku do kontynentalizmu klimatu oraz mezofity i higrofity, mezo- i eutrofy oraz acidofilne do bazyfilnych. Gatunkiem dominującym jest Calamagrostis epigejos (L.), rzadziej występuje Carlina vulgaris L., Centaurea phrygia L., C. scabiosa L., Daucus carota L. i Festuca rubra L.
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Authors and Affiliations

Wojciech Giża
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Abstract

Water mint (Mentha aquatica L.) belongs to the arsenic tolerant plant species suitable for cultivation

in Central European climate conditions. Therefore, its possible application for remediation of contaminated soil

was investigated in pot and field experiments. Two M. aquatica plants of different origin, i) commercially market-available mint plants, and ii) plants habituated at the arsenic contaminated former mining area in southern

Tuscany (Italy) were tested for their arsenic uptake, transformation, and speciation. The total arsenic concentrations in the experimental soils varied from 21 to 1573 mg As kg-1, the mobile fractions did not exceed 2% of total

soil arsenic. The mint plants originating from the contaminated area were able to remove ~400 µg of arsenic

per pot, whereas the commercial plant removed a significantly lower amount (~300 µg of arsenic per pot). Only

arsenite and arsenate, but no organoarsenic compounds were identified in both stems and leaves. Arsenate was

the predominant arsenic compound and reached up to 80% regardless of the origin of the mint plants. Although

M. aquatica seems to be able to grow in contaminated soils without symptoms of phytotoxicity, its efficiency to

remove arsenic from the soil is limited as can be demonstrated by total elimination of As from individual pots

not exceeding 0.1%. Moreover, the application of plants originating from the contaminated site did not result in

sufficient increase of potential phytoextraction efficiency of M. aquatica. Although not suitable for phytoextraction the M. aquatica plants can be used as vegetation cover of the contaminated soil at the former mining areas

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Authors and Affiliations

J. Száková
P. Tlustoš
W. Goessler
T. Pokorný
S. Findenig
J. Balík
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Abstract

To improve bioremediation of arsenic (As) contamination in soil, the use of microorganisms to efficiently reduce As and their assessment of genetic erosion by DNA damage using genomic template stability (GTS) evaluation and using RAPD markers were investigated. The five sites examined for microorganisms and contaminated soils were collected from affected gold mining areas. The highest As concentration in gold mining soil is 0.72 mg/kg. Microorganism strains isolated from the gold mining soil samples were tested for As removal capacity. Two bacterial isolates were identified by 16S rRNA gene sequence analysis and morphological characteristics as Brevibacillus reuszeri and Rhodococcus sp. The ability to treat As in nutrient agar (NA) at 1,600 mg/L and contaminated soil samples at 0.72 mg/kg was measured at 168 h, revealing more efficient As removal by B. reuszeri than Rhodococcus sp. (96.67% and 94.17%, respectively). Both species have the capacity to remove As, but B. reuszeri shows improved growth compared to the Rhodococcus sp. B. reuszeri might be suitable for adaptation and use in As treatment. The results are in agreement with their genetic erosion values, with B. reuszeri showing very little genetic erosion (12.46%) of culture in As concentrations as high as 1,600 mg/L, whereas 82.54% genetic erosion occurred in the Rhodococcus sp., suggesting that Rhodococcus sp. would not survive at this level of genetic erosion. Therefore, B. reuszeri has a high efficiency and can be used for soil As treatment, as it is capable to tolerate a concentration of 0.72 mg/kg and as high as 1,600 mg/L in NA.

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Authors and Affiliations

Lamyai Neeratanaphan
Tawatchai Tanee
Alongklod Tanomtong
Bundit Tengjaroenkul
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Abstract

The aim of the study was verification of the response of chamomile (Matricaria recutita (L.) Rauschert), peppermint (Mentha x piperita) lemon balm (Melissa officinalis L.), and sage (Salvia officinalis L.) on the elevated contents of inorganic As species in soils. The ability of herbs to accumulate arsenic was tested in pot experiment in which soils were contaminated by As(III) and As(V). The As(III), As(V), AB (arsenobetaine), MMA (monomethylarsonic acid) and DMA (dimethylarsinic acid) ions were successfully separated in the Hamilton PRP-X100 column with high performance-liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) techniques. The study examined total arsenic contents in soil and plants, as well as the mobility of the arsenic species from the soil into the studied plants. Peppermint demonstrated the highest arsenic concentration and phytoaccumulation among studied plants. The sequential chemical extraction showed that arsenic in the contaminated soil was mainly related to the oxide and organic-sulfide fractions. The results showed that the oxidized arsenic form had a greater ability to accumulate in herbs and was more readily absorbed from the substrate by plants. Research has shown that soil contaminated with As(III) or As(V) has different effects on the arsenic content in plants. The plant responses to strong environmental pollution varied and depended on their type and the arsenic species with which the soil was contaminated. In most cases it resulted in the appearance of the organic arsenic derivatives.

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Authors and Affiliations

Magdalena Jabłońska-Czapla
Rajmund Michalski
Katarzyna Nocoń
Katarzyna Grygoyć
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Abstract

Isatis cappadocica Desv. is a newly found As-hyperaccumulator showing very high remediation efficiency in polluted soils. We studied the effects of arsenic at 0-1400 μM concentrations on seed germination, relative root length, relative shoot height, and root and shoot biomass in young seedlings of I. cappadocica. The seeds were from Iranian arsenic-contaminated mine spoils and from a non-contaminated population. The control for reference was brassica (Descurenia sofia). Germination decreased significantly versus the control with increasing arsenic concentrations. The response to arsenic exposure differed between the I. cappadocica populations and D. sofia. I. cappadocica from mine spoil seeds showed strong resistance to the highest As concentration, with no adverse effects until the 1000 μM dose. Germination from non-mine seeds of I. cappadocica decreased to 89.6% at 1400 μM As. D. sofia germination was completely inhibited at 400 μM As. Relative root length (RRL) and relative shoot height (RSH) decreased with increasing As concentration. Overall, RRL correlated with RSH. Shoot height and root length were more sensitive to arsenic than other endpoints, and might be used as arsenic toxicity indicators. I. cappadocica showed more As tolerance than the reference brassica.

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Authors and Affiliations

Naser Karimi
Leila Siyahat Shayesteh
Hamidreza Ghasempour
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Abstract

Arsenic is one of the most harmful pollutants in groundwater. In this paper, the Nepali bio sand filter (BSF) was modi-fied with different bio-adsorbents, and proved to be an efficient method for arsenic removal from groundwater. Three dif-ferent bio-adsorbents were used to modify the Nepali BSF. Iron nails and biochar BSF, ~96% and ~93% arsenic removal was achieved, within the range of WHO guidelines. In iron nails, BSF and biochar BSF ~15 dm3∙h–1 arsenic content water was treated. In the other two BSFs, rice-husk and banana peel were used, the arsenic removal efficiency was ~83% of both BSFs. Furthermore, the efficiency of rice-husk and banana peel BSFs can be increased by increasing the surface area of the adsorbent or by reducing the flow rate.

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Authors and Affiliations

Ghulam S. Keerio
1
Hareef A. Keerio
2
ORCID: ORCID
Khalil A. Ibuphoto
3
Mahmood Laghari
1
Sallahuddin Panhwar
4
Mashooque A. Talpur
5

  1. Sindh Agriculture University, Department of Energy and Environment, Tandojam, Pakistan
  2. Hanyang University, Department of Civil and Environmental Engineering, Seoul, South Korea
  3. Sindh Agriculture University, Department of Farm Structures, Tandojam, Pakistan
  4. Mehran University of Engineering and Technology, US-Pakistan Centers for Advanced Studies in Water, Jamshoro, Pakistan
  5. Sindh Agriculture University, Department of Irrigation and Drainage, Tandojam, Pakistan
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Abstract

Arsenic is the only beneficial impurity for copper electrorefining through inhibiting anode passivation and the formation of floating slimes. The behaviour of copper anodes with different content of arsenic were studied at high current density (>280 A/m 2). It showed that low arsenic anodes (As < 300 ppm) easily generated anode passivation, floating slimes and cathode nodules during the electrorefining proccess. The floating slimes, electrolyte, cathode and anode were observed and analyzed. As result, low arsenic anodes were more likely to be passivated due to their microstructure defects and irregular microstructure. Increasing electrolyte temperature and addition of glycerol were propitious to reduce low arsenic anodes’ passivation. The floating slimes occured when the concentration of As(III) in electrolyte decreased to 1 g/L, and they would be precipitated by polyacrylamide. All measures greatly improved the cathode quality at current density of 300 A/m 2.
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Authors and Affiliations

Xuyong Zhang
1
ORCID: ORCID
Silei Chen
1
ORCID: ORCID
Lu Li
1
ORCID: ORCID
Peng Yang
1
ORCID: ORCID

  1. Jiangxi Copper Technology Institute Co., Ltd, Nanchang 330096, Jiangxi, PR China
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Abstract

Leaded and unleaded petrol samples as well as diesel oil samples were analysed lo determine Cd. Cr. Cu, Ni, Pb, Zn and As concentrations. In order lo obtain low detection limits new method of samples preparation was used. The fuel samples were dissolved in hydroraffinate which was the crude oil fraction obtained as a result of atmospheric distillation in the range of I 50---250°C. The obtained data on the metal concentrations in the investigated fuels allow determining the following emission factors of traffic fuels consumption processes [mg/kg fuel]: leaded and unleaded petrol - Cr - 0,5; Cu - 0,3; Ni - 0.5; Pb - 50 (leaded): Pb - 5 (unleaded); diesel fuel - Cd - 0,05: Cu - 0,3: Ni - 0.5. It was found in the investigations that traffic fuels consumption is not the source of Zn and As emission. The same refers to Cd emission in case of leaded and unleaded petrol consumption. On the basis of the identified emission factors Pb emission from traffic in Poland for years 1980---1999 as well as Cd, Cr, Cu and Ni emission for I 999 were assessed. The following emission in 1999 was determined as a result of the assessment [Mg]: Cd - 0,3: Cr - 2,9: Cu - 3,5 and Ni - 5,9. Emission of Pbu, was 237.6 Mg and Pb1.,w 79,2 Mg. These emissions were also compared with the total metal emissions in Poland.
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Authors and Affiliations

Stanisław Hlawiczka
Zofia Kowalewska
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Abstract

Popular statistical techniques, such as Spearman's rank correlation matrix, principal component analysis (PCA) and multiple linear regression analysis were applied to analyze a large set of water quality data of the Rybnik Reservoir generated during semiannual monitoring. Water samples collected at 9 sampling sites located along the main axis of the reservoir were tested for 14 selected parameters: concentrations of co-occurring elements, ions and physicochemical parameters. The aim of this study was to estimate the impact of those parameters on inorganic arsenic occurrence in Rybnik Reservoir water by means of multivariate statistical methods. The spatial distribution of arsenic in Rybnik Power Station reservoir was also included. Inorganic arsenic As(III), As(V) concentrations were determined by hydride generation method (HG-AAS) using SpectrAA 880 spectrophotometer (Varian) coupled with a VGA-77 system for hydride generation and ECT-60 electrothermal furnace. Spearman's rank correlation matrix was used in order to find existing correlations between total inorganic arsenic (AsTot) and other parameters. The results of this analysis suggest that As was positively correlated with PO43-; Fe and TDS. PCA confirmed these observations. Principal component analysis resulted in three PC's explaining 57% of the total variance. Loading values for each component indicate that the processes responsible for As release and distribution in Rybnik Reservoir water were: leaching from bottom sediments together with other elements like Cu, Cd, Cr, Pb, Zn, Ni, Ca (PC1) and co-precipitation with PO43-, Fe and Mn (PC3) regulated by physicochemical properties like T and pH (PC2). Finally, multiple linear regression model has been developed. This model incorporates only 8 (T, pH, PO43-, Fe, Mn, Cr, Cu, TDS) out of initial 14 variables, as the independent predictors of total As contamination level. This study illustrates the usefulness of multivariate statistical techniques for analysis and interpretation of complex environmental data sets.

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Authors and Affiliations

K. Widziewicz
K. Loska
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Abstract

In this research, the high arsenic content dust of copper smelting, as a raw material, the extraction of copper and arsenic from the high arsenic content dust in the leaching system containing acidic and alkaline compounds was investigated. Meanwhile, the effects of acid/alkaline initial concentration, liquid to solid ratio, leaching temperature, leaching time on the leaching rate of copper and arsenic were studied. The optimum conditions for the leaching of high arsenic content dust and preparation of copper arsenate were determined. The results showed that acidic/alkaline leaching of high arsenic content dust was particularly effective. 93.2% of the copper, and 91.6% of the arsenic were leached in an acidic leaching process and 95% of the arsenic, while less than 3% of the copper, less than 5% of the antimony, less than 2% of the bismuth was also leached in an alkaline leaching process. A new method (the parallel flow drop precipitate method) was developed in the synthesis of copper arsenate process. The parallel flow drop method was employed to adjust the molar ratio (copper to arsenic) of the mixed solution of the acid-leaching solution and the alkali-leaching solution by taking the drop acceleration of an acidic leaching solution and an alkaline leaching solution at 10 mL/min and 12 mL/min, at a temperature of 60°C and a reaction time of 1 h. Copper arsenate was prepared by mixing an acidic leaching solution and an alkaline leaching solution. The main phases of copper arsenate were CuHAsO4·1.5H2O and Cu5As4O15·9H2O. Copper arsenate contained 30.13% copper and 31.10% arsenic.

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Authors and Affiliations

W. Sheng
Y.-Y. Shen
Z. Sheng-Quan

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