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1.
A reversed‐phase fractionation method with subsequent biological and chemical analysis has been developed to estimate the contributions of the most potent estrogens to observed estrogenic effect potentials. Surface water samples were taken in the German Baltic Sea (Inner Wismar Bay and Darss Peninsula, sampling campaign July 2003) and were separated into seven individual fractions. Three fractions showed significant estrogenic activities and clear dose‐dependant responses were obtained in the yeast estrogen screen (YES). In the 2nd fractions liquid chromatographic‐electrospray‐tandem mass spectrometric (LC‐ESI‐MS‐MS) analyses showed the presence of bisphenol A (Inner Wismar Bay: 4.8 ng L–1 and 6 ng L–1; Darss Peninsula: 0.91 ng L–1 and 1.7 ng L–1) and ethinylestradiol (Inner Wismar Bay: 2.0 ng L–1 and 6.0 ng L–1; Darss Peninsula: < MDL and 1.7 ng L–1), whereas estrogenic activities in the YES were only around 10% of the positive control E2. Although not identified prior in the total extract the natural hormones estradiol (Inner Wismar Bay: 0.13 ng L–1 and 0.19 ng L–1; Darss Peninsula: 0.12 ng L–1 and 0.16 ng L–1) and estriol (Inner Wismar Bay: < MDL and 0.33 ng L–1; Darss Peninsula: < MDL) could be detected in the 3rd fractions, where high estrogenic potentials could be observed. The 4th fractions showed high responses as well and estrone were herein quantified with concentrations of 0.16 ng L–1 and 0.18 ng L–1 (Darss Peninsula) up to 0.37 ng L–1 (Inner Wismar Bay). Measured and calculated estradiol equivalents for individual fractions correlated very well (R2 = 0.78), when disregarding results of the 2nd fraction, where high deviations occurred.  相似文献   

2.
This paper presents the results from analyses of water samples from 15 Bulgarian reservoirs and lakes for detection of microcystins presence by high‐performance liquid chromatography (HPLC) coupled to a ultraviolet (UV) and photo diode array (PDA) detector. In 3 of the studied drinking water reservoirs cyanobacterial blooms were not detected. Cyanobacterial blooms were observed in 6 of 12 investigated water bodies used for fishing and water sports. Microcystis was the dominant cyanobacterial genus. The concentration of total microcystins in the biomasses ranged from 8 to 1070 μg g–1 (d.w.). Microcystin‐LR and microcystin‐RR were the predominant microcystins, followed by microcystin‐YR. Presence of dissolved microcystins was obtained in one water sample with concentration of total microcystins 1.64 μg L–1. Presence of microcystin‐LF and ‐LW or unknown peaks possessing characteristic microcystin‐like UV‐spectra were not detected. Those first results for occurrence of microcystins in some Bulgarian reservoirs and lakes are a contribution to the knowledge on their distribution.  相似文献   

3.
Trace metal clean sampling and analysis techniques were used to examine the temporal patterns of Hg, Cu, and Zn concentrations in shallow ground water, and the relationships between metal concentrations in ground water and in a hydrologically connected river. Hg, Cu, and Zn concentrations in ground water ranged from 0.07 to 4.6 ng L−1, 0.07 to 3.10 μg L−1, and 0.17 to 2.18 μg L−1, respectively. There was no apparent seasonal pattern in any of the metal concentrations. Filtrable Hg, Cu, and Zn concentrations in the North Branch of the Milwaukee River ranged from below the detection limit to 2.65 ng Hg L−1,0.51 to 4.30 μg Cu L−1, and 0.34 to 2.33 μg Zn L−1. Thus, metal concentrations in ground water were sufficiently high to account for a substantial fraction of the filtrable trace metal concentration in the river. Metal concentrations in the soil ranged from 8 to 86 ng Hg g−1, 10 to 39 μg Cu g−1, and 15 to 84 μg Zn g−1. Distribution coefficients, KD, in the aquifer were 7900,22,000, and 23,000 L kg−1 for Hg, Cu, and Zn, respectively. These values were three to 40 times smaller than KD values observed in the Milwaukee River for suspended particulate matter.  相似文献   

4.
Total arsenic concentrations have been measured in macroalgae specimens from two coastal areas of South Australia. Phaeophyta in both areas were found to contain elevated arsenic concentrations (42.2–179 μg g?1 and 26.3–65.3 μg g?1) relative to Rhodophyta (17.6–31.3 μg g?1 and 12.5–16.2 μg g?1) and Chlorophyta (6.3–16.3 μg g?1 and 9.9–10.8 μg g?1).  相似文献   

5.
Petroleum hydrocarbons in the sediments of the Bothnian Bay, Baltic proper, Öresund, Kattegatt and Skagerrak were analysed in a survey of oil pollution along the Swedish coast in 1974 and 1975. Sixty-one of these sediment stations were revisited in 1982 and analysed with the methods used in the first survey. The mean content of petroleum hydrocarbons (paraffin-naphthene fraction) in the sediment surface showed a statistically significant increase from 199 to 252 μg g?1 dry wt. The main increase had taken place in the coastal areas. Within 0–20 km distance of urbanized areas (>20 000 inhabitants) petroleum hydrocarbons had increased from 371 to 447 μg g?1. Sediment levels increased from 76 to 117 μg g?1, 20–50 km from urbanized areas. The increase in these areas was equivalent to 0.119 g m?2 yr?1.  相似文献   

6.
The plankton collected from three fish ponds shows a considerable variability within a pond, between the ponds and in the course of the year. The individual volumes or weights are (minimum—mean—maximum): Gleotrichia echinulata 41–252–879 μg3, Chlorella vulgaris 18–42–94 μm3, Oscillatoria amphigranulata 99–306–827 μm3, Brachionus plicatilis 1–4.918 μg, nauplia 0.5–1.25–2.35 μg, Mesocyclops hyalinus 4–45–369—μg, Heliodiaptomus viduus 41–202–288 μg, Daphnia carinata 186–1468–4578 μg.  相似文献   

7.
A solid‐phase extraction (SPE)‐gas chromatography (GC)‐mass spectrometry (MS) analytical method was developed for the simultaneous analysis of natural free estrogens and their conjugates in wastewater samples. Natural free estrogens and their conjugates in wastewater were successfully separated by the oasis hydrophilic‐lipophilic balance solid phase extraction (Oasis HLB SPE) method, and the conjugates were initially enzyme hydrolyzed by β‐glucuronidase or arylsulfatase from Helix pomatia prior to derivatization. N‐methyl‐N‐(tert‐butyldimethylsilyl)trifluoroacetamide (MTBSTFA) plus 1% tert‐butyldimetheylchlorosilane (TBDMCS) was chosen as the derivatization reagent, and the most appropriate conditions of derivatization were determined to be at 95°C for 90 min. The recovery ratios of nine target chemicals were determined by spiking them in 1 L of ultra‐purified water or the influent of a wastewater treatment plant (WWTP). The recovery ratios of six out of nine for the analytes ranged from 73.3–114.9% with relative standard deviations (RSD) from 1.6–19.9%. The established method was successfully applied to environmental wastewater samples which were collected from one municipal wastewater treatment plant (WWTP) in Osaka, Japan, for the determination of natural free estrogens and their conjugates. In the influent sample, E1, E2, E1‐3S, E3‐3S, and E1‐3G were detected at concentrations of 16.6, 9.6, 8.2, 21.9, and 3.2 ng L–1, respectively. However, only E1 was detected at a high concentration of 44 ng L–1 in the effluent sample, suggesting that it is the dominant natural free estrogen in the effluent.  相似文献   

8.
In the present article, a procedure for the simultaneous separation and preconcentration of trace amounts of cadmium and zinc is proposed. It is based on the adsorption of cadmium and zinc ions onto a column of Amberlite XAD‐4 resin loaded with aluminon reagent. Cadmium and zinc ions are quantitatively retained on the column in the pH range from 6.5–7.5, at a flow rate of 2 mL min–1. The cadmium and zinc ions are eluted with 5.0 mL of 5 mol L–1 HNO3 solution. Cadmium and zinc are measured by flame atomic absorption spectrometry (FAAS). In the present case, 0.1 μg of cadmium and 0.5 μg of zinc can be concentrated in the column from 1000 mL of aqueous sample, where their concentrations are as low as 0.1 and 0.5 ng mL–1, respectively. The relative standard deviations, for seven replicated determinations of 1.0 μg mL–1 of cadmium and zinc, are 1.2 and 1.1%, respectively. The detection limits for cadmium and zinc in the original solution are 0.02 and 0.11 ng mL–1, respectively. The interference of a large number of anions and cations has been studied and the optimized conditions are utilized for the determination of trace amounts of cadmium and zinc in different environmental and standard samples.  相似文献   

9.
Between January 1978 and September 1979 samples of subsurface (1 m) water and surface sediment were collected from sites in the North Sea, English Channel, Irish Sea and a number of estuarine areas. These have been analysed by fluorescence spectroscopy (UVF) in order to provide information on the levels of hydrocarbons generally present in UK marine waters.Total hydrocarbon concentrations (THCs) of water samples ranged from 1.1–74 μg l.?1 Ekofisk crude oil equivalents, all values greater than 3.5 μg l.?1 occurring inshore. In offshore areas the mean THCs were: 1.3 μg l.?1 in the northern North Sea, 1.5 μg l.?1 in the western Channel, 2.5 μg l.?1 in the eastern Channel and southern North Sea, and 2.6 μg l.?1 in the Irish Sea.THCs of sediment samples ranged from 0.27–340 μ g?1 dry weight Ekofisk crude oil equivalents, the highest concentration being in the Queen's Channel, the main entrance to the River Mersey.  相似文献   

10.
— The aims of this study were to estimate the total amount of mercury released to the environment during 60 years of gold mining (1867–1926) at Gympie, Queensland, Australia and to measure the mercury levels in soil samples surrounding the mining activity. We estimated that 1902 tonnes of mercury was released to the environment and about 1236 tonnes of which was released to the air. The mean mercury in the soil samples in the vicinity of the Scottish battery varied from 1.07 to 99.26 μg g?1 as compared to 0.075 μg g?1 as background mercury concentrations. The maximum mercury concentration measured in sediments of the Langton Gully was 6.12 μg g?1. These results show that large amount of mercury was used in this area during gold mining. Since mining is active in the area and Langton Gully flows into Mary River, we therefore, recommend that mercury concentration in air and fish should be monitored.  相似文献   

11.
In a survey in Greece from 1987 to 2000 hepatotoxic cyanobacterial blooms were observed in 9 out of 33 freshwaters. Microcystins (MCYSTs) were detected by HPLC in 7 of these lakes, and the total MCYST concentration per scum dry weight ranged from 50.3 to 1638 ± 464 μg g—1. Cyanobacterial genera (Microcystis, Anabaena, Anabaenopsis, Aphanizomenon, Cylindrospermopsis) with known toxin producing taxa were present in 31 freshwaters. From our data and a review of the literature, it would appear that Mediterranean countries are more likely 1) to have toxic cyanobacterial blooms consisting of Microcystis spp. and 2) to have higher intracellular MCYST concentrations. A case study in Lake Kastoria is used to highlight seasonal patterns of cyanobacterial and MCYST‐LR occurrence and to assess cyanotoxin risk. Cyanobacterial biovolume was high (> 11 μL L—1) throughout the year and was in excess of Guidance Level 2 (10 μL L—1) proposed by WHO for recreational waters and Alert Level 2 for drinking water. Further, surface water samples from April to November exceeded Guidance Level 3, with the potential for acute cyanobacterial poisoning. Intracellular MCYST‐LR concentrations (max 3186 μg L—1) exceeded the WHO guideline for drinking water (1 μg L—1) from September to November with a high risk of adverse health effects. Preliminary evidence indicates that in 3 lakes microcystins are accumulated in some aquatic organisms. Generally, a high risk level can be deduced from the data for the Mediterranean region.  相似文献   

12.
Total mercury concentrations were determined in a variety of fish and invertebrates and two dugongs from the coastal waters of Townsville on the N.E. coast of Australia. Fish generally contained the highest levels of mercury with 50% of the sharks examined having muscle concentrations above 0.5 μg g?1 wet weight. A significantly positive correlation was found between muscle levels and body length in sharks. Seventy per cent of the teleosts examined contained less than 0.2 μg g?1 in their muscle tissue and only 7% were above 0.5 μg g?1. Mercury concentrations in teleost liver were significantly positively correlated with muscle levels. Of the invertebrates examined, the cephalopod molluscs contained the highest levels although none exceeded 0.5 μg g?1. Mercury levels in the dugong were extremely low compared with most reported values for other marine mammals. It was concluded that the area contained mercury levels slightly above those considered normal for a non-contaminated marine environment.  相似文献   

13.
The concentration levels of Cd (25 ng l?1), Cu (0.45 μg l?1), Ni (0.48 μg l?1), Fe (0.2–7.0 μg l?1), Pb (40 ng l?1) and Zn (0.80 μg l?1) have been determined in the Danish Sounds and in the Kattegat. Different sampling techniques have been used and analyses have been carried out separately by two different investigators, both using freon-extraction followed by determination by atomic absorption spectrometry (a.a.s.). Except for iron, found mainly in the particulate phase, the metals are found predominantly in a dissolved and labile (extractable) form. The results are compared with trace metal levels found in the two main water masses entering the Kattegat—the North Sea and the Baltic Sea.  相似文献   

14.
Residues of diphenyl ether, a compound which has been used industrially for several decades, have been found in samples of seawater, lake water and snow (all in the ng I.?1 range) and in fat from fish, a seal and a gull (all in the μg g?1 range) collected from various points around Nova Scotia.  相似文献   

15.
This study was carried out to evaluate the occurrence of the fluoroquinolone antimicrobial agent ciprofloxacin (CIP) in the effluent of the Hospital of the Federal University of Santa Maria (HUSM). Measured environmental concentrations (MECs) of CIP in the hospital wastewater, both before (P1) and after (P2) cesspit/filter system treatment (CFTS), were determined by means of solid phase extraction and reversed‐phase liquid chromatography with fluorescence detection (LC‐FLD) and reversed‐phase liquid chromatography with mass spectrometric detection (LC‐MS/MS). The MECs (n = 7 daily composed samples) were 19 to 155 μg L–1 (average: 54 ± 21 μg L–1) and 32 to 99 μg L–1 (average: 65 ± 45 μg L–1) in P1 and P2, respectively. No relevant removal was observed from P1 to P2. In a worst case scenario, the final effluent was regarded as MECs of surface water. These MECs were generally 5 to 20,000‐fold higher than what was previously known. If the present data is drawn on to form a model of the situation in developing countries, the picture provides a first rough indication that the environmental risk associated with the use and emission of pharmaceuticals into the environment in developing countries might be higher than in developed countries.  相似文献   

16.
Major hurricanes Emily and Wilma hit the Mexican Caribbean in 2005. Changes in trace metals in the seagrass Thalassiatestudinum prior to (May 2004, 2005) and following passage of these hurricanes (May, June 2006) were determined at four locations along a ∼130 km long stretch of coast. Before the hurricanes, essential metals were likely limiting and concentrations of potentially toxic Pb were high in a contaminated lagoon (27.5 μg g−1) and near submarine springs (6.10 μg g−1); the likely sources were inland sewage disposal or excessive boat traffic. After the hurricanes, Pb decreased to 2.0 μg g−1 in the contaminated lagoon probably through flushing. At the northern sites, essential Fe increased >2-fold (from 26.8 to 68.3 μg g−1 on average), possibly from remobilization of anoxic sediments or upwelling of deep seawater during Wilma. Thus, hurricanes can be beneficial to seagrass beds in flushing toxic metals and replenishing essential elements.  相似文献   

17.
A cloud point extraction procedure is presented for the preconcentration and simultaneous determination of Ag+ and Pd2+ in various samples. After complexation with 2‐((2‐((1H‐benzo[d]imidazole‐2‐yl)methoxy)phenoxy)methyl)‐1H‐benzo[d]imidazol (BIMPI), which was used as a new chelating agent, analyte ions were quantitatively extracted to a phase rich in Triton X‐114 following centrifugation, and determination was carried out by flame atomic absorption spectrometry (FAAS). Under the optimum experimental conditions (i. e., pH = 7.0, 15.0·10–5 mol/L BIMPI and 0.036% (w/v) Triton X‐114), calibration graphs were linear in the range of 28.0–430.0 μg/L and 57.0–720.0 μg/L with detection limits of 10.0 and 25.0 μg/L for Ag+ and Pd2+, respectively. The enrichment factors were 35.0 and 28.0 for Ag+ and Pd2+, respectively. The method has been successfully applied to evaluate these metals in some real samples, including waste water, soil and hydrogenation catalyst samples.  相似文献   

18.
A stable extractor of metal ions was synthesized through azo linking of o‐hydroxybenzamide (HBAM) with Amberlite XAD‐4 (AXAD‐4) and was characterized by elemental analyses, IR spectral, and thermal studies. Its water regain value and hydrogen ion capacity were found to be 12.93 and 7.68 mmol g?1, respectively. The optimum pH range (with the half‐loading time [min], t1/2) for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were 2.0–4.0 (5.5), 2.0–4.0 (7.0), 2.0–4.0 (8.0), 4.0–6.0 (9.0), 4.0–6.0 (12.0), and 2.0–4.0 (15.0), respectively. Comparison of breakthrough and overall capacities of the metals ascertains the high degree of column utilization (>70%). The overall sorption capacities for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were found to be 0.29, 0.22, 0.20, 0.16, 0.13, and 0.11 mmol g?1 with the corresponding preconcentration factor of 400, 380, 380, 360, 320, and 320, respectively. The limit of preconcentration was in the range of 5.0–6.3 ng mL?1. The detection limit for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) were found to be 0.39, 0.49, 0.42, 0.59, 0.71, and 1.10 ng mL?1, respectively. The AXAD‐4‐HBAM has been successfully applied for the analysis of natural water, multivitamin formulation, infant milk substitute, hydrogenated oil, urine, and fish.  相似文献   

19.
Biologically configured ββ-hopanes, geologically configured αβ-hopanes and the biogenic hopenes were determined in dated sediment cores from Lake Fuxian in SW China and Lake Changdang in Eastern China in order to investigate anthropogenic influences on the abundance, composition and provenance of hopanoid hydrocarbons in lake sediments. Based on the results, hopenes were prevalent, with maximum values reaching 148.9 μg g−1 TOC in sediments of Lake Fuxian, an oligotrophic deep lake (average depth 89.6 m), where the long water column provided ample potential for the growth of hopene-producing bacteria especially the cyanobacteria. Sediment hopenes have diminished in abundance to values of 13.4–78.5 μg g−1 TOC in Lake Changdang, a eutrophic shallow (average 0.8–1.2 m) body, reflecting comparatively reduced importance of nutrient level on hopene production. Historical trends in hopenes input to the sediments of each lake are strongly dependent on nutrient status. During the last few decades, human-induced eutrophication has greatly boosted bacterial production, enhancing the accumulation of hopenes in sediments. Inputs of petroleum-derived αβ-hopanes were exceptionally high (average 71.2 μg g−1 TOC) in post-1968 sediments from Lake Changdang, their increase coinciding with the advent and acceleration of petroleum product use around the lake, in particular by fishing boats. Lake Fuxian on the other hand, has undergone slower economic development and the appearance of petroleum-derived αβ-hopanes in sediments was delayed to 1990 since when the average value has been 27.1 μg g−1 TOC. The abundance of αβ-hopanes in Lake Changdang has created a marked decrease in the relative contribution of hopenes to total hopanoids since 1968. Conversely, the amounts of αβ-hopanes introduced to Lake Fuxian since 1990 has yet to yield a clear change in the overall proportion of hopenes, but the abundance of ββ-hopanes has declined relative to total hopanoid levels for the period.  相似文献   

20.
In this study the occurrence of diclofenac and sub‐products in effluent emerging from the University Hospital at the Federal University of Santa Maria was investigated. One metabolite was identified and, in aqueous solution, three degradation products. The quantification was conducted by means of HPLC‐DAD, and the determination of metabolite and degradation products by LC–ESI–MS/MS–QTrap. For the HPLC‐DAD method, a 70:30 mixture of methanol/sodium phosphate was used in isocratic mode. For the LC–ESI–MS/MS–QTrap determinations, a mobile phase, where phase A was an ammonium acetate solution 5 × 10?3 mol L?1, and phase B was methanol (5 × 10?3 mol L?1)/ammonium acetate (9:1, v/v), on gradient mode. The LDs for the HPLC and LC–MS/MS methods, respectively, were 2.5 and 0.02 µg L?1, the LQs, 8.3 and 0.05 µg L?1, and the linear range from 10 up to 2000 µg L?1 and 0.05 up to 10 µg L?1. As expected, the LC–ESI–MS/MS–QTrap method was more sensitive and less laborious. The metabolite 4′‐hydroxy‐diclofenac was identified. Photolysis was used for the degradation studies and three products of diclofenac were identified (m/z of 214, 286 and 303) in aqueous solution. These results notwithstanding, no degradation products of diclofenac were found in the hospital effluent.  相似文献   

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