Mass flows of perfluorinated compounds (PFCs) in central wastewater treatment plants of industrial zones in Thailand

Perfluorinated compounds (PFCs) are fully fluorinated organic compounds, which have been used in many industrial processes and have been detected in wastewater and sludge from municipal wastewater treatment plants (WWTPs) around the world. This study focused on the occurrences of PFCs and PFCs mass flows in the industrial wastewater treatment plants, which reported to be the important sources of PFCs. Surveys were conducted in central wastewater treatment plant in two industrial zones in Thailand. Samples were collected from influent, aeration tank, secondary clarifier effluent, effluent and sludge. The major purpose of this field study was to identify PFCs occurrences and mass flow during industrial WWTP. Solid-phase extraction (SPE) coupled with HPLC-ESI-MS/MS were used for the analysis. Total 10 PFCs including perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluoropropanoic acid (PFPA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorohexane sulfonate (PFHxS), perfluoronanoic acid (PFNA), perfluordecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA) were measured to identify their occurrences. PFCs were detected in both liquid and solid phase in most samples. The exceptionally high level of PFCs was detected in the treatment plant of IZ1 and IZ2 ranging between 662-847 ng L⁻¹ and 674-1383 ng L⁻¹, respectively, which greater than PFCs found in most domestic wastewater. Due to PFCs non-biodegradable property, both WWTPs were found ineffective in removing PFCs using activated sludge processes. Bio-accumulation in sludge could be the major removal mechanism of PFCs in the process. The increasing amount of PFCs after activated sludge processes were identified which could be due to the degradation of PFCs precursors. PFCs concentration found in the effluent were very high comparing to those in river water of the area. Industrial activity could be the one of major sources of PFCs contamination in the water environment.     

Heavy Metal Contents of the Karasu Creek Sediments, Nigde, Turkey

Heavy metal contamination in sediments of the Karasu spring was investigated in the presented study. In this respect, sediment samples were collected from contaminant sites along the spring starting from the spring water manifestation site, base of the Akkaya dam to the dam exit site. Heavy metal concentrations were determined by X-ray Fluorescence Spectrometer. Cobalt, copper, arsenic, tin, nickel, zinc, cadmium, lead, aluminum, iron, titan, chromium and manganese contents of the Karasu creek sediments are found as 18.30–69.00, 12.40–595.0 5.50–345.3, 5.80–15.1, 10.9–64.1, 28.90–103,300, 4.1–356.2, 7.70–37,840, 13,460–109,400, 11,740–62,900, 22.18–59.04, 41.70–369 and 12.09–3,480 mg/kg, respectively. Results indicate the presence of a contamination in the Karasu creek. All the metal concentrations were found to be exceeding their acceptable limit values. Eutrophication is developed in the Karasu creek and the Akkaya dam. It is thought that heavy metal accumulation in the creek is originated from discharge from mine quarries, industrial and domestic wastes. Protection zones should be defined and all necessary measures must be taken along the Karasu creek.     

Extraction procedure optimization for perfluorooctane sulfonate and perfluorooctanoic acid in food packaging determination by LC-MS/MS

This research aimed to optimize the extraction method parameters for sample pretreatment and determine the levels of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) contamination in food packaging made of paper. Techniques used were pressurized liquid extraction (PLE) followed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Influence parameters of PLE were carefully evaluated for extracted concentration of samples in low level (ng g^?1). The study found that the optimal conditions for PLE were 30 min static extraction time with a flush volume of 100% cell volume and one extraction cycle at 80°C and 1,000 psi. The extraction technique validated the absolute recovery from PFOS and PFOA fortified control samples at three different levels (5, 50, and 200 ng g^?1), with seven repeats at each fortification level. The average recoveries were 79% or higher, with relative standard deviation (RSD) less than 11%. Optimization of the PLE method was established based on recovery data, accuracy, precision, and repeatability of the method. Using optimal PLE technique, PFOS and PFOA were extracted from 34 food-packaging samples collected in Thailand. PFOS and PFOA were detected in all kinds of collected samples, with average concentrations of 4.89 and 2.87 ng g^?1, respectively. The concentrations of PFOS and PFOA were highest in fast-food container samples: 36.99 and 9.99 ng g^?1, respectively.     

Trace metal levels and some chemical parameters in herby cheese collected from south eastern Anatolia-Turkey

Due to the consumption of the herby cheese in south eastern Anatolia-Turkey is at high ratio, chemical parameters such as dry matter, pH, acidity, aCl, protein, fat and trace metal contents in 50 different herby cheeses produced at this region have been determined in the presented study. The content of lead, copper, cobalt, nickel, chromium, cadmium, and iron have been analyzed by flame atomic absorption spectrometer in air/acetylene flame after combination ash digestion method and wet digestion method. The mean concentration of lead, copper, cobalt, nickel, chromium and cadmium in our samples are higher than literature values except iron.     

Determination and health risk assessment of enrofloxacin,flumequine and sulfamethoxazole in imported Pangasius catfish products in Thailand

The goals of this study were to determine the levels of three antibiotics – enrofloxacin, flumequine and sulfamethoxazole – in Pangasius catfish products imported into Thailand and to assess the health risks from consumption. To extract these antibiotic residues, acetonitrile, methanol and a small amount of formic acid were used as solvents. Determination of the antibiotics after extraction steps was carried out by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) technique. The results showed that 14 and 3 samples of Pangasius catfish products were contaminated with enrofloxacin and sulfamethoxazole, respectively. No flumequine residue was found. While the concentration levels of these antibiotics in most contaminated samples were lower than the European Union (EU) standard, one sample was found to contain sulfamethoxazole at 245.91 µg kg^?1, which was higher than the EU standard (100 µg kg^?1), indicating the likelihood that some contaminated freshwater fish products are widely distributed in Thai markets. Notably, the concentration levels of enrofloxacin in samples of Pangasius catfish with skin were higher than in non-skin products, suggesting that products with skin might retain more antibiotic residues than non-skin products. Although the hazard quotient showed that consuming imported Pangasius catfish products, based on the current consumption rate, will not adversely affect consumer health, antibiotic residues in Pangasius catfish products imported into Thailand should be continually monitored.     

Evaluation of trace heavy metal levels of some fish species sold at retail in Kayseri, Turkey

Cd, Ni, Cr, Zn, Cu and Pb concentrations of muscle tissue of 61 fish samples belonging to six fish species (Sparus auratus, Pomatomus saltatrix, Sarda sarda, Engraulis encrasicholus, Sander lucioperca, Scomber scombrus) retailed in Kayseri, Turkey were determined by flame atomic absorption spectrometry after wet digestion. Cd concentrations of at least 31 fish samples (50.8%) and Pb concentrations of at least six fish samples (9.8%) exceeded the corresponding Turkish permissible limit of 0.05 and 0.2 mg kg(-1) respectively whereas Zn concentrations of 11 fish samples (18%) exceeded the Turkish Food Codex limits of 50 mg kg(-1) for Zn. Cu concentrations of all fish species analyzed (100%) were below the corresponding Turkish legislations of 20 mg kg(-1). No limits were established concerning Ni and Cr concentrations in fish by the Turkish governmental authorities.     

Intramolecular Stable Isotope Ratios of N2O in the Tropical Swamp Forest in Thailand

 The dry-wet cycle is a common climatic phenomenon in the tropical regions of monsoon-affected Asia. An intermittent increase in N₂O was clearly observed in the Bang Nara River, with a tropical swamp catchment at the beginning of rainy season of November 1997. The intramolecular distribution of isotopes clearly demonstrated that nitrification is the major process for the production of N₂O. Using stable isotope data, the production mechanism of N₂O in the study areas was found to vary in time and space with changes in the redox boundary along the water flow. Received: 2 November 1999 / Accepted in revised form: 19 January 2000     

Evaluation of the adsorption behavior of mixed perfluoroalkyl and polyfluoroalkyl substances onto granular activated carbon and styrene-divinylbenzene resins

Because of the remarkable chemical structure of perfluoroalkyl and polyfluoroalkyl substances (PFAS), as well as the complex conditions of water, selecting an appropriate adsorbent for treating PFAS is critical. Adsorption needs to be environmentally friendly, low cost, and consider the types of adsorbents that work well in mixed PFAS solutions. In the present study, we used mixed PFAS to estimate the PFAS activity. This research aimed to evaluate and compare the efficacy of the adsorption of PFAS from water using different adsorbents: granular activated carbon (GAC), IRA 910 (strong anion resin), and DOWEX MB-50 (mixed exchange resin). Batch adsorption isotherms and kinetic studies were performed for perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), and perfluorohexane sulfonic acid (PFHxS). Freundlich models consistently described the kinetic behavior with a high correlation coefficient (R² > 0.98). PFAS adsorption capacities on GAC and IRA910 were dependent on the chain length (PFOS > PFOA > PFHxS). The adsorption capacity of DOWEX MB-50 decreased because of the sulfonate effects (PFOS > PFHxS > PFOA). The rate constants (k₂) that represented the adsorption of PFAS on different adsorbents observed within 96 h were accurately determined by the pseudo-second-order (PSO) model. GAC achieved followed the relationship k₂(PFOS) > k₂(PFOA) > k₂(PFHxS). Furthermore, k₂ of IRA910 decreased in the order of k₂(PFOA) > k₂(PFOS) > k₂(PFHxS), implying that IRA910 promoted hydrophobicity more significantly on the adsorption of PFCAs than perfluoroalkane (-alkyl) sulfonic acids. The kinetics of DOWEX MB-50 revealed k₂(PFHxS) > k₂(PFOS) > k₂(PFOA) because gel-type resins like DOWEX MB-50 are more suitable for shorter-chain PFAS. Further investigation is needed to determine the effect of organic matter under natural conditions and evaluate adsorptive selection caused by operational complexities.