Monitoring of Heavy Metals Content in Fish Muscle Tissue along the Sava River in Serbia

A multiresidue technique for extraction and gas chromatographic screening of 9 insecticide (lindane, heptachlor, aldrin, heptachlor epoxide, p,p'-DDE, dieldrin, endrin, p,p'-TDE, and p,p'-DDT) residues in catfish (Ictalurus punctatus) muscle tissue is presented. The 9 insecticides, plus dibutyl chlorendate internal standard, were fortified into catfish muscle tissue (0.5 g) and blended with 2 g C18 (octadecylsilyl derivatized silica reverse-phase material). The C18/muscle tissue matrix blend was fashioned into a column by adding the blend to a 10 mL syringe barrel containing 2 g activated Florisil. The insecticides were then eluted from the column with acetonitrile (8 mL), and a portion (2 microL) of the acetonitrile eluate was then directly analyzed by gas chromatography with electron capture detection. Unfortified blank controls were treated similarly. The resultant extracts contained pesticide analytes (31.25-500 ng/g) free of interfering compounds when analyzed. Correlation coefficients for the 9 extracted pesticide standard curves (linear regression analysis, n = 5) ranged from 0.9967 (+/- 0.0018) to 0.9999 (+/- 0.0001). Average percentage recoveries (82 +/- 4.8% to 97 +/- 3.6%, n = 25 for each insecticide), interassay (5.0 +/- 2.7% to 16.9 +/- 6.5%, n = 25 for each insecticide) and intraassay (1.8 to 4.7%, n = 5 for each insecticide) variabilities were indicative of an acceptable methodology for the analysis and screening of these residues in catfish muscle tissue.

A liquid chromatographic (LC) method was developed for the simultaneous determination of nitrofurazone (NFZ), nitrofurantoin (NFT), and furazolidone (FZD) in catfish muscle tissue. The drugs were extracted from the tissue with acetonitrile, and the lipids were removed from the extract with hexane. The acetonitrile extract was evaporated by rotary evaporation, and the resultant drug residues were dissolved with LC mobile phase. The mixture was sonicated, centrifuged, and filtered. The drugs were determined by using LC with a C18 reversed-phase (ODS Hypersil) column, a mobile phase of acetonitrile-1% aqueous acetic acid (25 + 75), and a photodiode array ultraviolet detector at 375 nm. NFZ, NFT, and FZD were each determined in catfish tissue at 5 fortification levels (80, 40, 20, 10, and 5 ng drug/g tissue). Average recoveries of each of the 3 drugs at each level ranged from 70.7 to 101.5%, and relative standard deviations ranged from 2.2 to 18.6%. The limit of detection of each drug was approximately 1 ng drug/g tissue, and the limit of quantitation was 5 ng drug/g tissue. In the second part of the study, the method was used to determine nitrofuran residues incurred in catfish tissue. Live channel catfish were intravascularly doses (10 mg/kg body wt) with NFZ to generate drug-incurred fish muscle tissue. Incurred NFZ levels exceeded 400 ng drug/g tissue at 2 h after dosing but decreased rapidly to approximately 1 ng drug/g tissue by 8 h after dosing, as determined by this method.

The muscle tissues of freshwater fish are a valuable source of protein, essential fatty acids, vitamins and minerals. In recent years, a man has actively explored the possibility of using these fabrics to develop innovative food products meeting the needs of modern consumers. The research aimed at studying the biological potential of the muscle tissue of Amur catfish Parasilurus asotus and Amur pike Esox reichertii. The object was frozen fish. The authors determined the nutritional value of freshwater fish of the Amur region water basin: the protein content in the muscle tissue of Amur catfish is 17.2 g/100 g, Amur pike is 18.4 g (22.6 and 24.2% of the daily protein requirement, respectively). The researchers specified amino acid protein composition of the muscle tissue of freshwater fish of the Amur region water basin and the amino acid score. They demonstrated that this muscle tissue contained an insufficient amount or an incorrect ratio of amino acids necessary to maintain health and normal functioning of the body. A man revealed the biological value of the lipid component and the fatty acid composition balance of the muscle tissue of the studied freshwater fish species of the Amur region water basin. The fatty acid composition analysis of lipids showed the prevalence of polyunsaturated fatty acids in them. Its content exceeded the value of the “ideal lipid” for the muscle tissue of catfish by 2 times and pike by 2.5 times.

The present investigations were conducted to examine the use of a new methodology termed matrix solid phase dispersion (MSPD) in combination with chromatographic techniques to analyze different classes of environmentally significant compounds in biological matrices. The research described in this dissertation represents the author's work to demonstrate the feasibility of improving environmental analytical methods by employing MSPD and chromatographic techniques in combination or separately. Preliminary tests were conducted to determine some of the parameters that would be used to test MSPD extraction techniques and to chromatograph standards and extracts of benzo (a) pyrene (BAP), benzo (a) pyrene ring-oxidized metabolites, Aroclor 1254 (PCB) and nine chlorinated pesticides. In each study, catfish (Ictalurus punctatus) muscle tissue (0.5g for each analysis) was fortified with either BAP, PCBs (Aroclor 1254) or nine chlorinated pesticides and subsequently mixed with 2.0 grams of octadecylsilyl derivatized silica (C$\sb{18}$) using a mortar and pestle. The resultant C$\sb{18}$-tissue blend was quantitatively transferred to a plastic 10 ml syringe and configured as a column. The target compounds were eluted from each column with a total of 8.0 ml of acetonitrile. These extracts were then subjected to a reverse-phase high pressure liquid chromatograph equipped with programmable ultraviolet-visible and fluorometric detectors for BAP analyses or a packed or capillary column gas chromatograph equipped with an electron capture detector for chlorinated pesticide or PCB analyses. In each study, catfish muscle tissue was fortified at six different concentrations (including a blank control) with five replicates run for each concentration. The tissue fortification levels for the BAP and the PCB studies were 0.20, 0.50, 1.0, 2.0, and 4.0 $\mu$g/g tissue sample. The tissue fortification levels for the chlorinated pesticide study were 31.3, 62.5, 125, 250, and 500 ng/g. The results from these studies demonstrated acceptable average relative percent recoveries of 74 $\pm$ 11% to 112 $\pm$ 13% for BAP, 59 $\pm$ 3.3 to 77 $\pm$ 9.5% for PCBs, and 82 $\pm$ 4.8% to 97 $\pm$ 3.6% for nine chlorinated pesticides.

The aim of this study was to determine the content of some elements (Pb, Cd, Hg, Fe, Cu, Zn, As) in muscle tissue of Prussian carp (Carassius auratus gibelio) from seven different lakes in the Belgrade region, Serbia. Concentrations of Pb, Hg and As in fish muscle tissues from all examined lakes were under the maximum residual levels prescribed by the European Union (EU) and the maximum allowed concentrations (MAC) for Serbia. In all investigated fish, levels of Cd exceeded maximum allowed concentrations (0.05 mg kg-1). Data on the finding of elements in fish speak concurrently about the safety of fish as food and are good indicators of environmental pollution.

Arsenic fractionation in sediments and speciation in muscles of fish, Chrysichthys nigrodigitatus from a contaminated tropical Lagoon, Nigeria

Fifty typical redevelopment industrial sites in the Putuo, Baoshan, Minhang, and Jiangding districts of Shanghai were chosen to evaluate the ecological risk of heavy metals in the soil. The contents of heavy metal (Hg, Cd, Pb, Cr, and As) in 1847 soil samples, taken from vertical sections, were determined, and their risks were evaluated using the Nemero composite index and Hakanson potential ecological risk index. The average contents of Hg, Cd, Pb, Cr, and As in topsoil samples were 0.33, 0.37, 74.55, 69.23, and 9.05 mg·kg-1, respectively. The contents of Hg, Cd, and Pb exceeded the soil background values of Shanghai, which were 2.75, 2.85, and 2.93 times the background values, respectively. The contents of five heavy metals in soil decreased gradually with increased depth. The contents of heavy metals in deep and saturated soils were close to, or below, the background values, indicating that the anthropic activity disturbance was mainly confined to the topsoil. The accumulation of Hg, Cd, and Pb was the most obvious in Putuo topsoil, with the average contents being 4.25, 4.85, and 3.09 times the background values, respectively. The average contents of Hg and Pb in Baoshan were 4.92 and 6.43 times the background values, respectively. The Nemero Composite Index of Baoshan and Putuo districts were 3.70 and 3.20, respectively, representing heavy pollution level at these sites. The Hakanson potential ecological risk indexes of the Putuo and Baoshang districts were 398.59 and 303.08, respectively, with considerable ecological risk levels. The content and ecological risk of heavy metals at the Minhang and Jiading sites were relatively low. In summary, the pollution of heavy metal in the redeveloped industrial sites is influenced by the operating time, industry type, and past management level of the enterprises. The heavy metal accumulation in the Putuo and Baoshan districts, whose industries developed earlier, were higher than those in the Minhang and Jiading districts. The pollution of heavy metal Hg, Cd, and Pb in soil should be a focus of future work.

The aim of this study was to investigate the presence of heavy metals/metalloids (Pb, Cd, Hg, Cu, Fe, Zn, As) in the muscle tissue of fish from the Danube River (two locations: Zemun and Grocka). For the purpose of heavy metal determination in fish muscle, 120 samples of six different fish species, Prussian carp, barbel, bream, carp, pike perch, and catfish were collected. For determining heavy metals, we used microwave oven digestion and atomic absorption spectrometer methods. The highest average content of Pb (0.084±0.004mgkg-1), Cd (0.082±0.003mgkg-1), Hg (0.466±0.006mgkg-1), and As (0.333±0.007mgkg-1) was found in the muscle of carp (an omnivorous fish) from Grocka, while the highest average level of Fe (13.60±0.03mgkg-1) was deposited in bream (also omnivorous) from Zemun. Also, the average Cu level (1.62±0.13mgkg-1) was the highest in catfish muscle (a carnivorous fish) from Grocka, while the highest Zn content (11.16±0.17mgkg-1) was determined in muscle of Prussian carp (an omnivorous fish) from Zemun. The highest content of heavy metals (Cu, Fe, and Zn, respectively) in muscle of the six different types of fish from both locations was symmetrically arranged by species (catfish, barbel, and Prussian carp, respectively). Concentrations of Pb, Hg, and As in the Danube River fish muscle were under the maximum residual levels prescribed by the European Union (EU) and the maximum allowed concentrations (MAC) for Serbia. On the other hand, in all fish muscle from both locations (Zemun and Grocka), higher concentrations of Cd than prescribed (MAC) were found, with the exception of bream and pike perch.

Heavy metal pollution is still present in the Danube River basin, due to intensive naval and agricultural activities conducted in the area. Therefore, continuous monitoring of this pivotal aquatic macro-system is necessary, through the development and optimization of monitoring methodologies. The main objective of the present study was to develop a prediction model for heavy metals accumulation in biological tissues, based on field gathered data which uses bioindicators (fish) and oxidative stress (OS) biomarkers. Samples of water and fish were collected from the lower sector of Danube River (DR), Danube Delta (DD) and Black Sea (BS). The following indicators were analyzed in samples: cadmium (Cd), lead (Pb), iron (Fe), zinc (Zn), copper (Cu) (in water and fish tissues), respectively, catalase (CAT), superoxide dismutase (SOD), glutathione peroxidase (GPx), malondialdehyde (MDA) (in fish tissues). The pollution index (PI) was calculated to identify the most polluted studied ecosystem, which revealed that Danube River is seriously affected by the presence of Fe (IP = 4887) and strongly affected by the presence of Zn (IP = 4.49). The concentration of Cd in fish muscle tissue was above the maximum permitted level (0.05 µg/g) by the EU regulation. From all analyzed OS biomarkers, MDA registered the highest median values in fish muscle (145.7 nmol/mg protein in DR, 201.03 nmol/mg protein in DD, 148.58 nmol/mg protein in BS) and fish liver (200.28 nmol/mg protein in DR, 163.67 nmol/mg protein, 158.51 nmol/mg protein), compared to CAT, SOD and GPx. The prediction of Cd, Pb, Zn, Fe and Cu in fish hepatic and muscle tissue was determined based on CAT, SOD, GPx and MDA, by using non-linear tree-based RF prediction models. The analysis emphasizes that MDA in hepatic tissue is the most important independent variable for predicting heavy metals in fish muscle and tissues at BS coast, followed by GPx in both hepatic and muscle tissues. The RF analytical framework revealed that CAT in muscle tissue, respectively, MDA and GPx in hepatic tissues are most common predictors for determining the heavy metals concentration in both muscle and hepatic tissues in DD area. For DR, the MDA in muscle, followed by MDA in hepatic tissue are the main predictors in RF analysis.

Heavy metals pollution and potential ecological health risk assessment in the Yangtze River reaches

Effect of Heavy Metals Pollution to Seawater Quality and Fishery Resources (Case Study on Fish Death in Jakarta Bay). Observation on heavy metals content in sea water were carried out in Jakarta Bay waters in May 2004. Heavy metals observed were Hg, Pb, Cd, Cu, Zn and Ni. This observation is conducted with fishes total death in this waters. Observation is done in Ancol beach 1 (3 stations), Ancol beach 2 (4 stations), Cilincing (3 stations), and Dadap River estuary (4 Station). The results showed that the average concentration of Hg, Cd and Cu in Ancol beach 1 were <0.001 ppm respectively, Pb is 0.001 ppm, Zn is 0.004 ppm, and Ni is 0.001 ppm. In Ancol beach 2 the average concentration of Hg, Cd, and Zn were <0.001 ppm, Pb is 0.002 ppm, Cu is 0.001 ppm and Ni 0.0017 ppm. In Cilincing the average concentration of Hg, Cd, and Zn were <0.001 ppm respectively, Pb and Cu were 0.002 ppm, and Ni was 0.0045 ppm. In Dadap River Estuary the average concentration of Hg and Cd were 0.001 ppm, Pb and Zn were 0.0027 ppm, Cu was 0.001 ppm, and Ni between 0.0012 ppm. The concentration of that sixth heavy metals in Ancol beach 1, 2, Cilincing, and Dadap River estuary still lower compared to the Threshold Value (TV) stated by The Office of StateMinistry for Life Environment (2004) for sea biota namely 0.001 ppm for Hg and Cd, 0.008 ppm for Pb and Cd, 0.05 ppm for Zn and Ni. That way the concentration of Hg, Pb, Cd, Cu, Zn, and Ni in Ancol beach 1, 2, Clilincing and Dadap estuary not danger for sea biota, while in Ancol beach 3, the average concentration of Hg, Pb, and Cd has danger for sea biota. Thereby total death of fishes in this waters not caused by heavy metals, but by others factors, one of that factors is blooming toxic phytoplankton which produced toxin where sea water change to be red, and this phenomena known as red tide. Keywords: Jakarta Bay, Heavy Metals, Pollution

This research is a quantitative descriptive study that aims to determine the heavy metal contamination of Pb and Hg. Sampling was carried out exploratively in the waters of Lekok Beach, Pasuruan Regency. The data obtained were analyzed by descriptive analysis by comparing the quality standards of the Minister of Environment Decree No. 51 of 2004. And analyzed by correlation test to determine the relationship between the content of heavy metals Pb and Hg in seawater and sediment with feather shells. The results of this study indicate that shellfish (Anadara antiquata) can accumulate heavy metals Pb and Hg. The average accumulation of heavy metals Pb and Hg in Anadara antiquata was 2,315 ppm and 1,100 ppm. The average heavy metal content of Pb and Hg along the sea waters of the Lekok coast are 0.204 ppm and 0.073 ppm. In the sediment the average metal content of Pb and Hg is 5.318 ppm and 1.215 ppm. The heavy metal content has exceeded the quality standard limit that has been determined by the Decree of the Minister of the Environment No. 51 of 2004 and RNO, so that it can be harmful to human health who consume shellfish. The results of the correlation test showed that there was a positive correlation between the heavy metal content of Pb and Hg in sediment and seawater and the heavy metal content of Pb and Hg in shellfish.

Metal concentrations in the muscle and liver tissues of fishes from the Erren River in southwestern Taiwan were analyzed to evaluate the pollution status after the completion of the restoration plan in 2000. It was the first time the tissue concentrations of 4 important elements, i.e. Fe, Mn, As and Hg, were reported in fishes from this area. Samples were collected in January 2002 at the junction of the Erren River and the Sanyegong River, the most polluted section of the river. Five fish species, Megalops cyprinoids (Indo-Pacific tarpon), Chanos chanos (milkfish), Liza macrolepis (large-scaled mullet), Mugil cephalus (striped mullet) and Orechromis sp. (tilapia) were collected. A total of 91 fishes were dissected and the muscle and liver tissues taken for analysis of seven metals, Fe, Zn, Cu, Mn, As, Hg and Cd, on a wet weight basis (mg/kg). Among them, Fe and Zn were the highest, followed by Cu, Mn and As, while the Hg and Cd concentrations were the lowest. Except for As and Hg, which showed higher concentrations in the muscle tissues than in the livers, the remaining elements showed higher concentrations in livers. Significant species differences were found in all elements and tissues. The highest concentrations of Fe, Zn, Cu and Mn in muscles were found in tilapia (4.04), striped mullet (4.38), large-scaled mullet (0.20) and milkfish (0.534), respectively. The highest concentrations of As and Hg were found in striped mullet (1.59) and Indo-Pacific tarpon (0.081), respectively. The highest concentrations of Fe (3122), Hg (0.045) and Cd (0.123) were found in livers of large-scaled mullet, while striped mullet had the highest concentration of Zn (77.6), Cu (78.2) and As (2.39). The level of Mn in tilapia was 1.32 mg/kg. The Zn, Cu and Cd concentrations of the muscles and livers were mostly 7-50% lower than the levels reported on the same species of the same tissue before the restoration indicating the improvement on the metal pollution status. The heavy metal concentrations in this area were similar to various uncontaminated areas around Taiwan and all were within the food standard levels of the FDA and NHMRC.

The presence of high concentrations of certain heavy metals (HMs) in drinking water poses a serious threat to the health of consumers. This work was done to investigate the concentration of heavy metals such as Arsenic (As) cadmium (Cd), chromium (Cr), iron (Fe), mercury (Hg), nickel (Ni), lead (Pb) and cobalt (Co) in the water resources of two cities of Iranshahr and Nikshahr in the south of Sistan and Baluchistan province. For this aim, 24 samples of drinking water sources were collected and the concentration of heavy metals was determined by inductively coupled plasma-mass spectrometry (ICP-MS). The results of samples of these networks showed that the average concentration of Pb (11.25 μg/L), Hg (10.33 μg/L), As (10.62 μg/L) and Cd (3.45 μg/L) far exceeds the standard of the World Health Organisation. The average concentration of heavy metals in the drinking water of Iranshahr and Nikshahr is respectively Fe>Pb>As>Hg>Ni>Cr>Co>Cd and Fe>Pb>As> Ni > Cr >Co>Cd> Hg. Potential sources of pollution in this study are attributed to infiltration of industrial effluents and agricultural runoff, which is a significant threat to groundwater quality. The calculated hazard quotients (HQ(values for non-carcinogenic risk show that this value is less than 1 in most metals, but the hazard index)HI) in children is greater than 1, and non-carcinogenic risk is evident. HI was obtained for children 5.4 and adults 2.6. However, the risk of carcinogenics in children and adults is equal to 2.66 E-05 and1.3E–6, respectively, and the increase in the risk of cancer in children is higher due to the consumption of drinking water. Therefore, it is necessary to protect water sources, water treatment and monitor more water distribution networks based on the water safety plan.

Potentially toxic elements in muscle tissue of different fish species from the Sava River and risk assessment for consumers