Analyses of phenolic compounds occurring in olive oil mill wastewaters by GC–MS

Phenolic compounds in olive oil mill wastewaters were analysed by HRGC–MS after extracting the acidified solution with ethyl acetate and derivatization with N,O-bis(trimethylsilyl)trifluoroacetamide. Both simple and complex phenols were detected with the latter being the most abundant. 1,2-dihydroxybenzene (catechol), p-hydroxyphenyl ethanol (tyrosol), 3,4-dihydroxyphenyl ethanol (hydroxytyrosol) and 4-hydroxy-3-methoxyphenyl ethanol (homovanillyl alcohol) predominated among the simple phenols using a gas chromatograph coupled with a mass selective detector.     

Polychlorinated-dibenzo-p-dioxins, -dibenzofurans and -dioxin-like polychlorinated biphenyls in aquatic organisms from lake Kasumigaura,Japan

Polychlorinated-dibenzo-p-dioxins (PCDDs), -dibenzofurans (PCDFs) and -dioxin-like polychlorinated biphenyls (DLPCBs) were determined in aquatic wildlife of Kasumigaura Lake (KUL), Japan from 1978 to 2001. Two plankton species elucidated several fold greater concentrations (2400–7800) than small tiger fish (310–6500), shrimp (160–1100), and three large fish namely, black bass (120–240), carp (94–120) and mullet (54) on pg/g fat. PCDD homologues were predominant accumulants with >68–<95% contribution and remaining was shared by PCDFs. Accumulation, non-ortho DLPCBs in plankton (3500–9200), shrimp (1600–8600) and small fish (2000–8800) and large fish (1300–3900) on ng/g fat basis were several orders magnitude greater than PCDD/DFs. The mono-ortho DLPCBs in large fish species were 23?000–83?000?ng/g fat and which it is accounted 94.3–95.9% the total dioxin-like PCBs accumulation. Temporal trends of PCDDs, PCDFs, non-ortho PCBs and TEQ in shrimp and small tiger fish were varied. The mullet had minimum toxic equivalency “TEQ” (14?pg?TEQ/g) followed by plankton Neomysis intermedia (25?pg?TEQ/g), small tiger fish (mean: 33, ranges 14–66?pg?TEQ/g), plankton Cyclopus vicinus (34?pg?TEQ/g), carp (mean: 35, ranges 32–38?pg?TEQ/g), shrimp (mean: 38, ranges 11–68?pg?TEQ/g) and black bass (mean: 59, ranges 38–79?pg?TEQ/g) on fat basis. In all the samples, PCDD was predominant TEQ contributor followed by PCDFs and DLPCBs. The contribution of mono-ortho DLPCBs to the total TEQ was 0.52–0.92 in large fish.     

Toxicity of cadmium to the green alga Parachlorella kessleri: Producing Cd-loaded algae for feeding experiments

The effects of Cd at environmental concentrations (0–32 µg/L) on the green alga Parachlorella kessleri were investigated. At about 3 µg Cd/L, toxic effects of Cd are becoming evident, much lower than reported previously. At 8 µg/L and higher, pronounced adverse effects on growth, cell morphology, size, and physiological state are seen. Therefore, levels lower than 2 µg Cd/L should be employed to produce Cd-carrying algae for feeding experiments with organisms on the next trophic level, e.g. mussels, to avoid reduced food uptake. These findings also suggest that aquatic ecosystem conditions can be indirectly influenced via the impairment of the nutritional value of algae since they are the basic organisms of aquatic food chains.     

Standard purity and response factors of perfluorinated compounds

It has been reported that the relative response factors of isotopically labeled standards and unlabeled standards of the same perfluorinated compounds could be different. Individual (100 ng mL^?1) solutions of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) were analyzed using high-performance liquid chromatography tandem mass-spectrometry under negative-ion electrospray to detect any impurities present down to 0.5%–0.1% relative to the major component. Purity of the standards ranged from approximately 86% to ≥ 97%. Standard solutions of unlabeled and isotopically labeled materials were analyzed to compare the response factors of isotopically labeled analytes versus their nonlabeled counterparts in three different matrices at equivalent concentrations: organic solvent (methanol), serum extract, and water present individually and concurrently. Not all labeled analytes have the same response factor as their nonlabeled complement, and in at least one case the matrix in which the standard is present may cause significant suppression of response. Standard solutions of electrochemical fluorination produced PFOA and PFOS were quantified under multiple reaction monitoring mode, using calibration curves prepared from standards consisting primarily of linear standards only. The use of linear only standards may cause under-prediction of concentrations, and that the working range of these standards may be limited.     

Evaluation of pesticides multiresidue contamination of khat leaves from Jazan region,Kingdome Saudi Arabia,using solid-phase extraction – gas chromatography/mass spectrometry

The habit of khat chewing is widespread with a deep-rooted sociocultural tradition in these regions and as such poses a public health problem. The use of pesticides is considered to be indispensable practice for the production of adequate food supply for the increasing demands by the global population and for control of insect-borne diseases. Thus, contamination of the environment with pesticides and entry of these chemicals into the food chain is unavoidable especially in developing countries. The main objective of our current study was to assess pesticide pollution of khat leaves (unknown origin) obtained while being smuggled into the Kingdom of Saudi Arabia and to be used in Jazan area. A total of 120 khat leaf samples were extracted using solid-phase extraction followed by gas chromatography/mass spectrometry analysis for the presence of 69 standard pesticides using an internal standard, tiphenyl phosphate. No pesticide residues were detected in all the studied samples. These data as preliminary and more experiments need to be performed to confirm our present findings. Routine monitoring of the pesticide residues is important for the prevention, control, and reduction of environmental pollution and also for legal decisions to minimize health risks.     

Investigation of naphthalene contamination in olive oil from Greece

Abstract

Incidents of using naphthalene in olive orchards as a repellent of olive fly (Bactrocera oleae) have recently been recorded. Naphthalene, the primary ingredient of mothballs, is described to be diluted in plastic bottles and hanged on the trees releasing its characteristic odor which is supposed to repel olive fly. Since naphthalene has been characterized as possibly carcinogenic to humans and animals, it was considered essential to monitor olive oils regarding their potential contamination with this specific pollutant. To this goal, a simple, sensitive and reliable analytical method for the determination of naphthalene in olive oil has been developed. The method involves extraction with ethyl acetate: acetonitrile (1:1) and determination of naphthalene using gas chromatography triple quadrupole mass spectrometry. The method was validated in four fortification levels, 0.005, 0.01, 0.05, and 0.1?mg/kg in accordance with the EU requirements. The obtained results were acceptable as far as validation criteria are concerned, given recoveries between 71% and 87% and RSDs between 5% and 24%. The limit of determination for naphthalene was set at 0.005?mg/kg based on the lowest concentration level being validated with acceptable accuracy. The analytical technique was successfully applied to 75 olive oil samples collected from oil mills in Greece and no positive results of naphthalene were detected.     

Occupational exposures,delivered doses and exposure limits for chromium and nickel†

The interaction of HCH (50 mg/kg) and dietary protein levels on microsomal drug metabolizing enzymes system and liver lipids were studied in the rats for 90 days. The results indicated that rats fed a lower protein diet and HCH has a higher rate of mortality, lower rate of growth and an increased liver weight. A significant induction in the hepatic microsomal aminopyrine‐N‐demethylase, p‐nitroanisole‐O‐dealkylase, benzo(a)pyrene hydroxylase and glutathione‐S‐transferase activity was observed in pesticide treated animals as compared to control animals. The pathological changes observed in liver of HCH treated animals consisted mainly of necrosis and fatty degeneration of hepatocytes. HCH also induced the significant accumulation of cholesterol, triglycerides, phospholipid and total lipid in liver in low protein diet animals. Protein accelerates the metabolism of HCH, resulting in a decrease of HCH concentration with the increase of dietary protein level. A close correlation existed between lipid accumulation, induction of drug metabolizing enzyme system and deposition of HCH in liver.     

Gas chromatographic studies of chlorinated phenols,chlorinated anisoles,and chlorinated phenylacetates

The g.l.c. retention times of all chlorinated phenols, anisoles, and phenylacetates on different capillary columns are presented. The relative retention times of the chlorinated phenols are discussed with reference to their pK_a values and their toxicities.     

Removal of pesticides from water samples by adsorption with fatty acids supported on barium sulphate

Oleic or linoleic acid supported on barium sulphate was used to remove atrazine and terbuthylazine in the range of 0.1–2.0 μg/L using spiked water samples. The sorption of atrazine depends on the stirring time and the best value is 150 min. Terbuthylazine is removed well with a stirring time of 60 min and its adsorption is about 90%. Detection of the residual pesticide in treated waters, after solid phase extraction (SPE), was carried out by GC‐MS operating in selected ion monitoring (SIM) using a calibration curve by direct injection of standard solutions of herbicide.