Application of HS-SPME in the determination of potentially toxic organic compounds emitted from resin-based dental materials

Leaching of volatile substances from resin-based dental materials may have a potential impact on the biocompatibility as well as safety of these materials. Information from manufacturers on ingredients in the materials is very often incomplete. Patients and dentists may be in contact with components emitted from cured dental fillings or from substrates applied in their preparation. Therefore, determination of the components of these materials is necessary for better prevention from possible harmful effects caused by dental fillings. The aim of this work was the isolation and identification of organic compounds evolved from four commercial resin-modified glass-ionomer cements (resin-based dental materials applied in dentistry) by using an alternative method of volatile compounds analysis-HS-SPME (headspace-solid phase microextraction). Dental materials were heated in closed vial at various temperatures and volatile substances released into the headspace phase above the sample were isolated on a thin polymeric fibre placed in SPME syringe. Identification was performed by using the GC-MS (gas chromatography-mass spectrometry) technique. Almost 50 RMGIC (resin-modified glass-ionomer cement) components (monomers and additives) were identified. The main identified leachables were: iodobenzene (DPICls-diphenyliodonium chloride degradation product), camphorquinone (photo-initiator), tert-butyl-p-hydroxyanisole (inhibitor), 4-(dimethylamino)ethyl benzoate (co-initiator), ethylene glycol dimethacrylate (monomer).     

Levels of lead, cadmium, copper, iron, and zinc in deciduous teeth of children living in Irbid, Jordan by ICP-OES: some factors affecting their concentrations

The aim of this study was to measure the concentrations of lead (Pb), cadmium (Cd), copper (Cu), iron (Fe), and zinc (Zn) in deciduous teeth from children living in Jordan and to investigate the affecting factors. Deciduous teeth samples (n?=?320, without fillings) were collected from 5- to 12-year-old children and analyzed for Pb, Cd, Cu, Fe, and Zn using inductively coupled plasma–optical emission spectrometry. A questionnaire was used to gather information on each child, such as sex, age, tooth type (incisors, canines, and molars), tooth position within the mouth (upper or lower jaw), caries status, presence of amalgam fillings inside the mouth, type of drinking water (tap water, home purified water, and plant purified water), and zone of residence (close to or far from heavy traffic roads). The mean concentrations of Pb, Cd, Cu, Fe, and Zn were 30.26, 0.55, 6.23, 34.72, and 128.21 μg/g, respectively. Our results indicate that there is a clear relation between the concentrations of the metals analyzed in this study and tooth type, tooth position within the mouth, caries status, presence of amalgam fillings inside the mouth, and type of drinking water. No significant differences in the concentrations of the five metals analyzed were observed due to sex. Our results also show that no significant difference among Pb, Cd, Cu, Fe, and Zn concentrations and age among the ages of 5–6, 7–8, 9–10, and 11–12, except for Pb, which decreases at age 11–12.     

Effect of teeth amalgam on mercury levels in the colostrums human milk in Lenjan

Human milk is usually the only source of food for infants during the first 4 to 5 months of their life. Maternal environmental mercury exposure is directly related to fish consumption or amalgam filling. In this research, 38 human milk samples were collected from mothers of Lenjan area who were not occupationally exposed with mercury. Mercury concentration in human milk was determined by AMA254 Mercury Analyzer. A level of mercury was examined in relation to somatometric, demographic and dental amalgam parameters. Obtained results showed that only dental amalgam significantly increased the mercury level in human milk (p < 0.001). The mean mercury concentrations in milk of mothers without teeth fillings (n = 13), with one to three teeth fillings (n = 10), and four to eight teeth fillings (n = 15) were 2.87, 5.47, and 13.33 μg/l, respectively. The result of this study also showed a positive correlation of mercury milk levels with the number of teeth fillings of the mother (p < 0.05, r = 0.755). The estimated weekly intake of mercury of a breastfed infant in this study was, in some cases, higher than provisional tolerance weekly intake recommended by FAO/WHO, which pose a threat to their health.     

Rapid analysis of tile industry gaseous emissions by ion mobility spectrometry and comparison with solid phase micro-extraction/gas chromatography/mass spectrometry

The present paper reports on a rapid method for the analysis of gaseous emissions from ceramic industry, based on ion mobility spectrometry (IMS) as a means for on-site monitoring of volatile organic compounds (VOCs) produced during tile baking. IMS was calibrated with a set of reference compounds (i.e. ethyl acetate, ethanol, ethylene glycol, diethylene glycol, acetaldehyde, formaldehyde, 2-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 1,3-dioxolane, 1,4-dioxane, benzene, toluene, cyclohexane, acetone, acetic acid) via air-flow permeation. The technique was tested on a laboratory-scale kiln and tiles prepared with selected glycol- and resin-based additives. Finally, the analytical method was applied to emissions from two industries in the Modena (Italy) ceramic area. The results of all experimental phases were compared to those obtained by solid phase micro-extraction/gas chromatography/mass spectrometry (SPME/GC/MS). IMS showed potential as a real-time monitoring device for quality assessment in ceramic industry emissions. IMS spectra, SPME/GC/MS data, relationship between additives/baking conditions and produced VOCs and advantages and limitations of both techniques will be discussed.     

The influence of denture cleansers on the release of organic compounds from soft lining materials

Biocompatibility constitutes the most fundamental requirement with respect to all dental materials to be applied within the oral cavity. In its environment, various toxic compounds may be released by dental materials which pose potential threats to the patient's health. Due to the fact that dentures remain in the oral cavity for a very long time, a detailed examination and verification of prosthetic materials with a view to their toxicity seems to be essential. By using very sensitive measurement techniques such as gas chromatography, one may determine which compounds are released by these materials. The aim of this paper was to determine the influence of various denture cleansers on the release of organic compounds from four soft dental materials used in prosthetics for lining dentures. These materials when placed in commonly used disinfectants (Corega Tabs, sodium hypochlorite, chlorhexidine, hydrogen peroxide), as well as in artificial saliva, produced 13 chemical compounds such as monomers (methyl methacrylate, ethyl methacrylate, dodecyl methacrylate), plasticizers (dibutyl phthalate, diethyl phthalate, tributyl acetylcitrate) and others (e.g. benzophenone). A comparison of chemical compounds released from acrylic-based materials and those released from silica-based materials demonstrated that acrylic-based materials are less resistant to disinfectants.     

Pharmaceuticals as emerging organic contaminants in Umgeni River water system,KwaZulu-Natal,South Africa

The occurrences of pharmaceuticals and personal care products as emerging organic contaminants (EOCs) have been reported in several countries of the world except from African countries. This study was therefore conducted to investigate the occurrence of nine antibiotics, five antipyretics, atenolol, bezafibrate, and caffeine in wastewater and surface water samples from the Umgeni River. The water samples were extracted with solid-phase extraction using hydrophilic-lipophilic balance (HLB) and C-18 cartridges for the acidic and neutral drugs, respectively. The quantification was carried out with high-performance liquid chromatography-diode array detector (HPLC-DAD) using the standard addition method. The method limits of detections were in the range of 0.14–0.97 μg/L while the recoveries were between 53.8 and 108.1 %. The wastewater had 100 % occurrence of the analytes studied, with caffeine having the highest concentration at 61?±?5 μg/L and nalidixic acid being the most observed antibiotic at 31?±?3 μg/L. The waste treatment process reduced the influent concentrations by 43.0–94.2 % before discharge except for atenolol removal that is lower. The concentrations of the analytes were lower in the surface water with most compounds having concentrations below 10 μg/L except acetaminophen and atenolol. The estuary mouth and Blue Lagoon had the highest concentrations of some of the compounds in surface water which depict downstream load. The factors governing the fate and mobility of these compounds in this environment are not fully understood yet and will require further studies.     

Spatial distribution and quantification of endocrine-disrupting chemicals in Sado River estuary, Portugal

The important Portuguese Sado River estuary has never been investigated for the presence of potentially endocrine-disrupting chemicals (EDCs), such as natural estrogens (estradiol, estrone), pharmaceutical estrogens (17α-ethynylestradiol), phytoestrogens (daidzein, genistein and biochanin A), or industrial chemicals (4-octylphenol, 4-nonylphenol, and bisphenol A). Thus, the main objective of this study was to evaluate their presence at 13 sampling points distributed between both the industrial and the natural reserve areas of the estuary, zones 1 and 2, respectively. For that, water samples collected in summer and winter were processed by solid phase extraction and analyzed by high-performance liquid chromatography with photodiode array detection and gas chromatography–mass spectroscopy. Results showed that estrone, ethynylestradiol, all the aforementioned phytoestrogens as well as bisphenol A and 4-octylphenol were found in zone 1. In zone 2, neither estrogens nor 4-OP were found. However, in the same zone, daidzein (500 ng/L) and genistein (320 ng/L) attained their highest levels in summer, whereas biochanin A peaked in winter (170 ng/L). Furthermore, bisphenol A was also found in some areas of zone 2, but showed similar concentrations in both surveys (about 220 ng/L). This study demonstrated that the Sado River estuary had low EDCs levels, suggesting that the Sado’s high hydrodynamic activity may be involved in the dilution of local pollution. It was suggested that at the current levels of concentrations, all assayed EDCs are unlikely to individually cause endocrine disruption in local animals. However, under a continuous exposure scenario, an additive and/or synergistic action of the estrogenic chemicals load can not be excluded, and so, continuous monitoring is advisable.     

Occurrence of naproxen,ibuprofen, and diclofenac residues in wastewater and river water of KwaZulu-Natal Province in South Africa

The present paper reports a detailed study that is based on the monitoring of naproxen, ibuprofen, and diclofenac in Mbokodweni River and wastewater treatment plants (WWTPs) located around the city of Durban in KwaZulu-Natal Province of South Africa. Target compounds were extracted from water samples using a multi-template molecularly imprinted solid-phase extraction prior to separation and quantification on a high-performance liquid chromatography equipped with photo diode array detector. The analytical method yielded the detection limits of 0.15, 1.00, and 0.63 μg/L for naproxen, ibuprofen, and diclofenac, respectively. Solid-phase extraction method was evaluated for its performance using deionized water samples that were spiked with 5 and 50 μg/L of target compounds. Recoveries were greater than 80% for all target compounds with RSD values in the range of 4.1 to 10%. Target compounds were detected in most wastewater and river water samples with ibuprofen being the most frequently detected pharmaceutical. Maximum concentrations detected in river water for naproxen, ibuprofen, and diclofenac were 6.84, 19.2, and 9.69 μg/L, respectively. The concentrations of target compounds found in effluent and river water samples compared well with some studies. The analytical method employed in this work is fast, selective, sensitive, and affordable; therefore, it can be used routinely to evaluate the occurrence of acidic pharmaceuticals in South African water resources.     

Endocrine disrupting chemicals in New Orleans surface waters and Mississippi Sound sediments

Endocrine disrupting compounds (EDCs), represented by steroid hormones, organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and bisphenol A have been determined in four sediment cores from the Gulf of Mexico, from New Orleans surface water (Lake Pontchartrain and Mississippi River), and from the influent and effluent of a New Orleans municipal sewage treatment plant. During the five-month monitoring of selected EDCs in the Mississippi River (MR) and Lake Pontchartrain (LP) in 2008, 21 of 29 OCPs in MR and 17 of 29 OCPs in LP were detected; bisphenol A was detected in all of the samples. Steroid hormones (estrone, 17β-estradiol and 17α-ethinylestradiol) were detected occasionally. Total EDC (OCPs + PCBs + steroid hormones + bisphenol A) concentrations in the two surface water samples were found to vary from 148 to 1112 ng L(-1). Strong correlation of the distribution of total OCPs, total PCBs and total EDCs between solid and water phases was found in LP, while moderate or no correlation existed in MR. OCPs, PCBs, steroid hormones, and bisphenol A were all detected in the ocean sediments, and total EDCs were measured in the range of 77 to 1796 ng g(-1) dry sediment weight. The EDCs were also found in untreated and treated municipal sewage samples with a removal efficiency of 83% for OCPs but no removal efficiency for 17α-ethinylestradiol.     

Multi-component analysis of polar water pollutants using sequential solid-phase extraction followed by LC-ESI-MS

A multi-component screening analysis method for polar to medium-polar water pollutants was developed. Sample clean-up and group separation are performed by sequential solid-phase extraction (SSPE) using automated SPE with C18 and polymeric sorbent materials. Analyses are performed by liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS) using a single-quadrupole instrument. More than 90 priority compounds of environmental interest--comprising the most important chemical and substance classes: phenols, carboxylic acids, aromatic sulfonates, aromatic amines, pharmaceuticals, surfactants, dyes, and pesticides--have been chosen for the experiments. The compounds are divided by the SSPE procedure into 3 different polarity classes. The extraction recoveries were determined in the 3 fractions for every single substance, and were for most of the analytes in the range of 50-100%. A mixture of hexane-dichloromethane was used for the elution of nonpolar compounds like alkylphenols from C18. Methanol and acetone are well suited for the elution of more polar substances. The limits of detection (LODs) were determined for all compounds. Effluents from municipal and industrial wastewater treatment plants (WWTPs) treating waste water from textile industries; and the corresponding receiving waters (rivers and lakes) have been analysed with the developed method. Urban and industrial pollution was observed in rivers and streams in the area north of Milan, Italy. In the water samples different phenols (nitrophenols, bisphenol A, nonylphenol), alkylphenol ethoxylate surfactants, their metabolites with endocrine disrupting potential, aromatic sulfonates, linear alkylbenzenesulfonate surfactants, dyes, pesticides, pharmaceuticals, and a dichlorobenzidine compound were identified.     

Occurrence and removal efficiencies of eight EDCs and estrogenicity in a STP

The occurrence and removal of eight endocrine disrupting compounds (EDCs), including estrone (E(1)), 17β-estradiol (E(2)), estriol (E(3)), 17α-ethinylestradiol (EE(2)), diethylstilbestrol (DES), bisphenol A (BPA), nonylphenol (NP) and octylphenol (OP), and their estrogenicities were investigated in a sewage treatment plant in Harbin city, China. The EDCs were extracted from wastewater samples by solid phase extraction (SPE) method and analyzed with gas chromatography coupled with mass spectrometry (GC-MS). The average concentrations in the influents and effluents ranged from 6.3 (EE(2)) to 1725.8 ng L(-1) (NP) and from 相似文献   

Dental Fluorosis in Wild Deer: Its Use as a Biomarker of Increased Fluoride Exposure

The relationships between age (range: 3 to 14 yr), mandibular bone fluoride level (marker of accumulated internal dose, range: 597 to 4680 mg F^- kg^-1> dry wt) and intensity of dental fluorosis (reflecting fluoride exposure during enamel formation) were studied in a sample of 53 fluorosed red deer from a fluoride-polluted area in the Czech-German border region (Ore mountains and their southern foreland). Assessment of the severity of dental fluorosis was performed for the 3 permanent premolars and 3 molars of one hemimandible per animal by using an ordinal measurement scale. For statistical analysis, the maximum tooth score of fluorosis (MTS) and the dental lesion index of fluorosis (DLI, sum of the six tooth scores per individual) were used. In the sample, both MTS (r_s = 0.850) and DLI (r_s = 0.813) were highly significantly (p <0.00001) correlated with bone fluoride content. A weaker correlation existed between age and bone fluoride content (r_s = 0.322, p <0.05). The results demonstrate that in case of regional, long-term fluoride pollution, dental fluorosis (measured as MTS or DLI) can be used as a sensitive biomarker of fluoride exposure in deer and thus as an indicator of the level of environmental contamination by fluorides. In many countries, skulls and mandibles of wild deer are regularly and continuously collected by hunters. Assessment of the prevalence and severity of dental fluorosis in this material offers the opportunity for an efficient large-scale biomonitoring of environmental pollution by fluorides at very low cost.     

Anionic surfactant linear alkylbenzene sulfonates (LAS) in sediments from the Gulf of Gdańsk (southern Baltic Sea, Poland) and its environmental implications

Linear alkylbenzene sulfonate (LAS) is a group of anionic surfactants employed in the formulation of laundry and cleaning products, with a global production rate of 4 million metric tons. Sediments from the Polish coast of the southern Baltic Sea were collected at ten stations. Total LAS concentrations, measured by high-performance liquid chromatography, were between 0.04 and 0.72 mg LAS·kg(-1) dry weight. Highest LAS concentrations were found in suspended matter collected from the Vistula River, sediment collected close to the Vistula River mouth and from the Gdańsk Deep, known as the depositional area. With the obtained environmental LAS concentrations, a risk assessment for this surfactant has been carried out, based on publicly available acute and chronic toxicity data in target organisms. The results indicated that LAS could pose a low risk for the existing benthic community applying worst case scenario assessment. This is the first time that levels of LAS have been measured in environmental samples of the southern Baltic Sea.     

Estrogenic chemicals and estrogenic activity in leachate from municipal waste landfill determined by yeast two-hybrid assay

Estrogenic activity and estrogenic chemicals in landfill leachate were investigated by yeast two-hybrid assay and chemical analysis. Leachate sample extracted by liquid-liquid extraction with dichloromethane at pH 7.0 showed a higher dose-response curve than sample extracted at pH 3.0. or than sample extracted by solid phase extraction at either pH 7.0 or 3.0. The fraction extracted at pH 3.0 specifically inhibited not only growth of yeast but also estrogenic activity in this assay, suggesting that it contained anti-estrogenic chemicals. The greatest contributor to estrogenic activity among the chemicals identified in leachate extract was bisphenol A, with an estimated contribution ratio of 84%. The contribution ratios of 4-nonyl phenol (4-np) and 4-tert-octyl phenol (4-t-op) were estimated at 1.0%, and 0.1%, respectively, while natural estrogens such as 17beta-estradiol or estrone were below detection limit, so that their contribution ratio was estimated at no more than 10%. The estrogenic activity of leachate was decreased by aeration treatment alone after 7 days, and was no longer detected after 22 days. Concentrations of bisphenol A, 4-np and 4-t-op likewise decreased with aeration.     

Identification and quantification of 19 pharmaceutical active compounds and metabolites in hospital wastewater in Cameroon using LC/QQQ and LC/Q-TOF

Human pharmaceutical residues are a serious environmental concern. They have been reported to have eco, geno, and human toxic effects, and thus their importance as micropollutants cannot be ignored. These have been studied extensively in Europe and North America. However, African countries are still lagging behind in research on these micropollutants. In this study, the wastewaters of the University Teaching Hospital of Yaoundé (UTHY) were screened for the presence of active pharmaceutical ingredients and their metabolites. The screening was carried out using two methods: high-performance liquid chromatography coupled to a triple quadrupole analyzer (LC/QQQ) and high-performance coupled to a mass spectrometer with a time of flight analyzer (LC/Q-TOF). A total of 19 active pharmaceutical ingredients and metabolites were identified and quantified. The compounds identified include paracetamol (211.93 μg/L), ibuprofen (141 μg/L), tramadol (76 μg/L), O-demethyltramadol (141 μg/L), erythromycinanhydrate (7 μg/L), ciprofloxacin (24 μg/L), clarinthromycine (0.088 μg/L), azitromycine (0.39 μg/L), sulfamethoxazole 0.16 μg/L), trimetoprime (0.27 μg/L), caffeine (5.8 μg/L), carnamaeepine (0.94 μg/L), atenolol (0.43 μg/L), propranolol (0.3 μg/L), cimetidine (34 μg/L), hydroxy omeprazole (5 μg/L), diphenhydramine (0.38 μg/L), metformine (154 μg/L), and sucralose (13.07 μg/L).     

Seasonal distribution, source investigation and vertical profile of phenolic endocrine disrupting compounds in Dianchi Lake, China

Phenolic endocrine disrupting compounds, including nonylphenol-di-ethoxylate (NP2EO), nonylphenol-mono-ethoxylate (NP1EO), 4-nonylphenol (4-NP), bisphenol A (BPA), 4-cumylphenol (4-CP) and 4-tert-octylphenol (4-t-OP), were investigated in water, surface sediment and sediment cores in Dianchi Lake to track their seasonal distributions, pollution sources and historical trends. The concentrations of NP2EO, NP1EO, 4-NP, BPA, 4-CP and 4-t-OP were up to 295.14, 448.48, 45.28, 530.33, 8.96 and 21.37 ng L(-1) in water, and up to 297.11, 809.63, 4.58, 166.87, 3.62 and 40.69 ng g(-1) dry weight in surface sediment, respectively. Except BPA in water, concentrations of all the other phenolic compounds in both of the matrices were higher in January than in July, 2011. The concentrations decreased significantly with an increase in distance from the sampling locations which were adjacent to the urban areas (Kunming City, Chenggong City and Jinning City). The pollution of phenolic EDCs came mainly from industry, agriculture and daily life. The relationships between the concentrations of target compounds and the six water quality parameters were evaluated. There were significant positive correlations between concentrations of phenolic compounds in water and in surface sediment. For sediment cores, three clearly separated maxima occurred in segments 0-5 cm (the late 2000s), 5-10 cm (the early and mid of 2000s) and 20-25 cm (the mid of 1980s), respectively. NP2EO, NP1EO and BPA were the three dominant compounds in the lake.     

Accumulation of endocrine disrupting chemicals (EDCs) in the polychaete Paraprionospio sp. from the Yodo River mouth,Osaka Bay,Japan

This study presents the levels of endocrine disrupting chemicals (EDCs) accumulated by Paraprionospio sp. from the Yodo River mouth, Osaka Bay. Since high concentrations of nonylphenol (NP), bisphenol A (BP), octylphenol (OP), 17β-estradiol (E2), and estrone (E1) have been measured in sediment from Osaka Bay, some bioaccumulation could be expected particularly in benthic animals. EDCs were analysed in Paraprionospio sp., a dominant benthic species in Osaka Bay. The results showed that Paraprionospio sp. had accumulated varying concentrations (wet weight; w.w.) of NP at 1,460–4,410 ng/g; BP at 22.5–39.6 ng/g; OP at 18.9–45.4 ng/g; E2 at 0.89–4.35 ng/g; and E1 at 0.06–2.50 ng/g. Accumulation of NP and OP were highest among the samples gathered in summer (July 2008), while concentrations of BP, E2, and E1 did not much differs within 3 years. EDC levels in Paraprionospio sp. were apparently greater than those in sediments showing bioaccumulation.     

Dietary exposure to xenoestrogens in New Zealand

Continuing evidence of the feminising effects of xenoestrogens on a range of wildlife species increases the need to assess the human health risk of these estrogen mimics. We have estimated the exposure of New Zealand males, females and young men to a range of naturally occurring and synthetic xenoestrogens found in food. Only estrogenic compounds that act by interaction with the estrogen receptor have been included. Theoretical plasma estrogen activity levels were derived from estrogen exposure estimates and estrogenic potency data. Theoretical plasma levels were compared with published data for specific xenoestrogens. There was surprisingly close agreement. Xenoestrogenicity from dietary intake was almost equally attributed to naturally occurring and synthetic xenoestrogens. Relative contributions for a male, for example were isoflavones (genistein and daidzein) (36%) and bisphenol A (34%) with smaller contributions from alkyl phenols (18%) and the flavonoids (phloretin and kaempferol) (12%). It is suggested that dietary xenoestrogens might have a pharmacological effect on New Zealand males and postmenopausal women, but are unlikely to be significant for pre-menopausal women.     

毛细管柱气相色谱法测定水中痕量拟除虫菊酯杀虫剂

采用石油醚萃取水样 ,萃取液经氮气吹扫浓缩后 ,用气相色谱仪对水样中拟除虫菊酯杀虫剂——甲氰菊酯、三氟氯氰菊酯 (功夫 )、高效氯氰菊酯、氰戊菊酯、溴氰菊酯进行了定量测定。由于毛细管柱的高柱效和微池 ECD的高灵敏度 ,使得上述目标组分与水样中的其它杂质能达到较好的分离 ,即使含量极低也能被检出。本方法省去了样品萃取液的净化处理这一步骤 ,可较快地测定拟除虫菊酯杀虫剂 ,在污染事故应急监测方面具有实用性。