Evaluation of a tape-stripping technique for measuring dermal exposure to pyrene and benzo(a)pyrene

Epidemiological studies have shown an increased incidence of cancer among workers occupationally exposed to polycyclic aromatic hydrocarbons (PAHs). As the dermal route is considered important for exposure to PAHs in the workplace, the aim of this study was to develop and evaluate a tape-stripping technique for monitoring dermal exposure to pyrene and benzo(a)pyrene. The tape-stripping method was evaluated by applying different concentrations of pyrene and benzo(a)pyrene directly onto tape strips (spiked tapes), clean glass plates, and on the skin of five volunteers. The glass plates were stripped using a single strip of tape and the skin of the volunteers was stripped with five consecutive strips of tape after 0 and 30 minutes. The method was also tested on five chimney sweeps at three exposure sites. High-performance liquid chromatography with fluorescence detection was employed for the quantification of pyrene and benzo(a)pyrene. The mean recovery from the spiked tapes was 97% for pyrene and 93% for benzo(a)pyrene. The mean overall recovery from the glass plates was 88% and 76% for pyrene and 88 and 85% for benzo(a)pyrene. The recovery from human skin was 70% and 63% for pyrene and 60 and 54% for benzo(a)pyrene, after 0 and 30 minutes, respectively. A concentration gradient was clearly detected between the five consecutive strips. Detectable amounts of pyrene and benzo(a)pyrene were found on all chimney sweeps at all exposure sites. This method can thus be used to detect and quantify dermal exposure to pyrene and benzo(a)pyrene. The results also show that pyrene and benzo(a)pyrene may be taken up by the skin.     

Sorption and desorption of benzo(a)pyrene in aquatic systems

The sorptive behaviour of polycyclic aromatic hydrocarbons (PAHs) is critical to controlling their transport, fates and effects in the environment. Experiments are described which detail the behaviour of a model compound (benzo(a)pyrene) under simulated aquatic conditions. The kinetics of sorption were comparable to those of other PAH compounds. The sorption equilibrium was extensively studied and found to be affected by several key parameters, notably sediment concentration. The sorption coefficient decreased substantially with the sediment concentration, from 9580 ml g(-1) at a sediment concentration of 0.067 g l(-1) to 1,110 ml g(-1) at a sediment concentration of 9.8 g l(-1). The results are consistent with previous reports and often explained by the presence of colloids. In this paper the dry weight concentration of colloids was determined and used for deriving the true sorption coefficient, which is up to an order of magnitude higher than the observed partition coefficient. The sorption of benzo(a)pyrene was also dependent on some of the particle properties, and the sorption coefficient was found to increase with the organic carbon content and specific surface area of sediment particles. The desorption of benzo(a)pyrene from sediment was shown to be relatively rapid, with implications for the potential remobilisation of benzo(a)pyrene and similar compounds.     

地表水超痕量苯并(a)芘的检测及空白干扰消除

采用液液萃取-超高效液相色谱仪接荧光检测器测定地表水中超痕量的苯并(a)芘,并对方法空白的干扰因素进行探讨。研究发现,该法的空白干扰主要来自于溶剂二氯甲烷,溶剂经蒸馏提纯后可消除干扰。以重新蒸馏提纯的二氯甲烷为提取剂,方法的检测限为0.05 ng/L,加标回收率为87.4%~132%,且空白测定值低于方法检出限,可满足地表水中超痕量苯并(a)芘检测的需求。     

In situ laser-induced fluorescence (LIF) analysis of petroleum product-contaminated soil samples

General considerations of the calibrations of in situ measurements are presented and the concept of using an "average oil" with average analysability for calibration purposes is introduced. The in situ analysis of 30 petroleum product-contaminated soil samples with laser-induced fluorescence (LIF) spectroscopy was performed. Compared to an uncontaminated laboratory reference (LR) soil, 23 soil samples exhibited significantly higher LIF signals, so that these soil samples were classified as contaminated. The repeatability and reproducibility of the in situ LIF analysis were investigated. For the calibration of the LIF data, two LR oils (a fuel oil and a crude oil) were employed. The degree of soil contamination with petroleum products ranged from the limit of detection (LOD) for LIF analysis (ca. 100 ppm), or below, to more than 10,000 ppm. The petroleum product concentrations determined with in situ LIF analysis reveal a reasonable correlation with the results of standard IR analysis after extraction of the contaminated soils.     

Benzo(a)pyrene induced structural and functional modifications in lung cystatin

Cystatins are thiol proteinase inhibitors ubiquitously present in the mammalian body. They serve a protective function to regulate the activities of endogenous proteinases, which may cause uncontrolled proteolysis and damage. In the present study, the effect of benzo(a)pyrene [BaP] on lung cystatin was studied to explore the hazardous effects of environmental pollutant on structural and functional integrity of the protein. The basic binding interaction was studied by UV-absorption, FT-IR, and fluorescence spectroscopy. The enhancement of total protein fluorescence with a red shift of 5 nm suggests structural scratch of lung cystatin by benzo(a)pyrene. Further, ANS binding studies reaffirm the unfolding of the thiol protease inhibitor (GLC-I) after treating with benzo(a)pyrene. The results of FT-IR spectroscopy reflect perturbation of the secondary conformation (alpha-helix to β-sheet) in goat lung cystatin on interaction with BaP. Finally, functional inactivation of cystatin on association with BaP was checked by its papain inhibitory activity. Benzo(a)pyrene (10 μM) caused complete inactivation of goat lung cystatin. Benzo(a)pyrene-induced loss of structure and function in the thiol protease inhibitor could provide a caution for lung injury caused by the pollutants and smokers.     

Earthworm cytochrome P450 determination and application as a biomarker for diagnosing PAH exposure

We developed a new microsome purification method and used the Omura and Sato method to measure the total content of cytochrome (Cyt) P450 in earthworm (Eisenia fetida) microsomes. In method development, two different pretreatments, i.e. solubilization or manual separation were used to purify worm microsomes. Solubilization was more effective than manual separation and difference spectra showed a peak at 450 +/- 1 nm in microsomes received solubilization pretreatment. We conducted a 48 h contact test by exposing worms on pyrene (Py) and benzo[a]pyrene (BaP) spiked filter paper. A dose-response relationship was established between total P450 content and the concentration of Py or BaP ranging from 10(-6) mg mL(-1) to 10(-2) mg mL(-1). Results show that total Cyt P450 content in earthworms is a promising biomarker for diagnosing PAHs exposure at sublethal dose ranges.     

Multistep, microvolume resin fractionation combined with 3D fluorescence spectroscopy for improved DOM characterization and water quality monitoring

Conventionally, resin fractionation (RF) method has been widely used to characterize dissolved organic matter (DOM) found in different source waters based on general and broad DOM fractions grouping. In this study, a new refined method using multistep, microvolume resin fractionation combined with excitation emission matrix fluorescence spectroscopy (MSM-RF-EEMS) was developed for further isolation and characterization of subfractions within the primary DOM fractions separated from using the conventional RF method. Subsequently, its feasibility in indicating the occurrence of urban pollution in source waters was also assessed. Results from using the new MSM-RF-EEMS method strongly illustrated that several organic subfractions still exist within the regarded primary pure hydrophobic acid (HoA) fraction including the humic- and fulvic-like organic matters, tryptophan- and tyrosine-like proteins. It was found that by using the MSM-RF-EEMS method, the organic subfractions present within the primary DOM fraction could be easily identified and characterized. Further validation on the HoA fraction using the MSM-RF-EEMS method revealed that the constant association of EEM peak T1 (tryptophan) fraction could specifically be used to indicate the occurrence of urban pollution in source water. The correlation analysis on the presence of EEM peak T2 (tyrosine) fraction could be used as a supplementary proof to further verify the presence of urban pollution in source waters. These findings on using the presence of EEM peaks T1 and T2 within the primary HoA fraction would be significant and useful for developing a sensory device for online water quality monitoring.     

液相色谱法测定土壤中苯并(a)芘

用快速溶剂萃取法ASE300对土壤样品进行前处理,以配有荧光检测器的高效液相色谱仪分析土壤样品中苯并(a)芘的含量,该方法以乙腈、水梯度比例混合作为流动相,流速为1.0 ml/min;激发波长和发射波长分别为255 nm和420 nm;保留时间为27.58 min。样品的称样量为25 g时,测定检出限为8.28×10-5mg/kg,相对标准偏差(RSD)为1.0%~12%,回收率为60%~87%,以上指标均能满足环境中土壤样品的检测要求。     

Mechanism of ofloxacin fluorescence quenching and its interaction with sequentially extracted dissolved organic matter from lake sediment of Dianchi,China

The wide use and occurrence of antibiotics in water environments have caused wide concerns. Ofloxacin (OFL) was selected as a target antibiotic, and the interaction between OFL and sequential extracted dissolved organic matter (DOM) from the sediment of Dianchi, a hypertrophic lake in Southwest China, was explored using fluorescence quenching technology. The method of fuorescence quenching was used to characterize the interaction between OFL and sequentially extracted DOM. The result indicated that static and dynamic quenching both existed in the interaction. The interaction in the background water (0.01 mol/L NaCl and 200 mg/L NaN₃) became increasingly weak with the further extraction of DOM. A low non-linear factor N value (0.53～0.63) of Freundlich model was observed, indicating a non-linear interaction between OFL and DOM. Elemental characterization and infrared spectrum analysis showed an enhanced OFL-DOM binding with the decrease in humic acid (HA) polarity. The effect of ion strength was tested in the OFL-DOM interaction to show the impact of usually existing metal ions in water environment on the OFL behavior. The result showed that K⁺ had little influence, but Cu²⁺ had a significant promotion (p?相似文献   

Simultaneous determination of p-arsanilic acid and roxarsone in feed by liquid chromatography-hydride generation online coupled with atomic fluorescence spectrometry

A novel, simple and sensitive liquid chromatography-hydride generation online coupled with atomic fluorescence spectrometry (LC-HG-AFS) method was developed for simultaneous determination of p-arsanilic acid (p-ASA) and roxarsone in feed. 20% Methanol aqueous was used as extraction reagent, after preprocessing samples by ultrasonic oscillation, then injected into the chromatography Waters symmetry shield RP18 analytical column (150mm x 4.6mm, 5 microm), finally detected by an atomic fluorescence spectrometer. The calibration curves of analyses were linear over a range of concentrations (0.2-4mg L-1 and the correlation coefficients were higher than 0.9990. The limits of detection were 0.2 mg L-1. The method has been validated by linearity, precision and recovery. p-ASA and roxarsone in feed can be successfully and simultaneously determined using the developed method without a tedious pretreatment procedure.     

土壤中苯并[α]芘的准确度控制指标研究

通过全国多家实验室的大量监测数据,研究分析了土壤中苯并[α]芘测定的准确度控制指标,并与EPA8270D进行了比较,旨在为环境监测工作提供质量控制依据和指标。研究表明,标准样品测定的相对误差控制范围0～56.4%,实际样品加标回收率为55.8%～115%。     

Application of a compact all solid-state laser system to the in situ detection of atmospheric OH,HO2, NO and IO by laser-induced fluorescence

A tuneable, high pulse-repetition-frequency, solid state Nd:YAG pumped titanium sapphire laser capable of generating radiation for the detection of OH, HO2, NO and IO radicals in the atmosphere by laser induced fluorescence (LIF) has been developed. The integration of the laser system operating at 308 nm into a field measurement apparatus for the simultaneous detection of hydroxyl and hydroperoxy radicals is described, with detection limits of 3.1 x 10(5) molecule cm(-3) (0.012 pptv in the boundary layer) and 2.6 x 10(6) molecule cm(-3) (0.09 pptv) achieved for OH and HO2 respectively (30 s signal integration, 30 s background integration, signal-to-noise ratio = 1). The system has been field tested and offers several advantages over copper vapour laser pumped dye laser systems for the detection of atmospheric OH and HO2 radicals by LIF, with benefits of greater tuning range and ease of use coupled with reduced power consumption, instrument footprint and warm-up time. NO has been detected in the atmosphere at approximately 1 ppbv by single photon LIF using the Alpha 2Sigma+ <-- Chi 2Pi1/2 (0,0) transition at 226 nm, with absolute concentrations in good agreement with simultaneous measurements made using a chemiluminescence analyser. With some improvements in performance, particularly with regard to laser power, the theoretical detection limit for NO is projected to be approximately 2 x 10(6) molecule cm(-3) (0.08 pptv). Whilst operating at 445 nm, the laser system has been used to readily detect the IO radical in the laboratory, and although it is difficult to project the sensitivity in the field, an estimate of the detection limit is < 1 x 10(5) molecule cm(-3) (< 0.004 pptv), well below previously measured atmospheric concentrations of IO.     

Effects of salinity and organic matter on the partitioning of perfluoroalkyl acid (PFAs) to clay particles

The influence of salinity and organic matter on the distribution coefficient (K(d)) for perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in a brackish water-clay system was studied. The distribution coefficients (K(d)) for PFAs onto inorganic clay surfaces increased with salinity, providing evidence for electrostatic interaction for the sorption of PFAs, whereas the relationship between K(d) and organic carbon content (f(oc)) suggested that hydrophobic interaction is the primary driving force for the sorption of PFAs onto organic matter. The organic carbon normalized adsorption coefficient (K(oc)) of PFAs can be slightly overestimated due to the electrostatic interaction within uncoated inorganic surfaces. In addition, the dissolved organic matter released from coated clay particles seemed to solvate PFA molecules in solution, which contributed to a decrease in K(d). A positive relationship between K(d) and salinity was apparent, but an empirical relationship for the 'salting-out' effect was not evident. The K(d) values of PFAs are relatively small compared with those reported for persistent organic pollutants. Thus, sorption may not be a significant route of mass transfer of PFAs from water columns in estuarine environments. However, enhancement of sorption of PFAs to particulate matter at high salinity values could evoke potential risks to benthic organisms in estuarine areas.     

Energy-dispersive X-ray fluorescence analysis of moss and soil from abandoned mining of Pb-Zn ores

This research investigates heavy metal pollution around one of the most important mining areas in Turkey, the Sebinkarahisar (Giresun) lead–zinc mining, by means of analyzing moss and soil samples collected in the neighborhood of the copper mining at different distances. Energy dispersive X-ray fluorescence spectrometry (Epsilon 5, PANalytical, Almelo, The Netherlands) is utilized in the experiments. The results have indicated that the both moss and soil samples contain aluminum, vanadium, chromium, manganese, iron, nickel, copper, zinc, arsenic, barium, cerium, tungsten, and lead. The comparison of the heavy metal concentrations with the typical measurements in the world and with the limit values for the human health has revealed the critical heavy metal pollution levels in the region. The possible consequences of these results are briefly discussed from the point of potential hazards to ecology and human health.     

Rapid,ultra-sensitive detection of gas phase elemental mercury under atmospheric conditions using sequential two-photon laser induced fluorescence

We have examined the sensitivity of sequential two photon laser induced fluorescence (LIF) detection of elemental mercury, Hg(0) in the gas phase. The most sensitive approach involves an initial laser excitation of the 6(3)P1-6(1)S0 transition at 253.7 nm, followed by excitation with a second laser to the 7(1)S0 level. Blue shifted fluorescence is observed on the 6(1)P1-6(1)S0 transition at 184.9 nm. The excitation scheme, involving sequential excitation of two atomic transitions, followed by detection of the emission from a third is extremely specific and precludes detection of anything other than atomic mercury. Using our 10 Hz laser system we have achieved a detection sensitivity of 0.1 ng m(-3) at a sampling rate of 0.1 Hz, i.e. averaging 100 laser shots at a pressure of one atmosphere in air. At low concentrations we sampled simultaneously with an automated mercury analyzer (Tekran 2537A), to ensure accuracy. We have examined the linearity of the technique, generating flows containing mercury concentrations between 1 and 10,000 ng m(-3) using a permeation tube and dynamic dilution, but relying on the concentrations given by the Tekran at low levels and the concentration calculated from dilution at high levels. We find that the detection is linear over the five orders of magnitude that we were able to vary the concentration. Our measured detection limits in He and Ar are much lower as these gases are inefficient fluorescence quenchers.     

Application of cryofocusing hydride generation and atomic fluorescence detection for dissolved mercury species determination in natural water samples

The concentration levels of mercury (Hg) species in natural water samples are usually low. Consequently, accurate analysis with low detection limits is still a major problem. In this work, a method was applied for the simultaneous direct determination of dissolved mercury species in water samples by on-line hydride generation (HG), cryogenic trapping (CT), gas chromatography (GC) and detection by atomic fluorescence spectrometry (AFS). The suitability of the method for real samples with different organic matter and chloride contents was evaluated by recovery experiments in synthetic and natural spiked water samples. The HG method was compared with other current available methods for mercury analysis with respect to the different fraction of mercury analysed, i.e. 'reactive', 'reducible' or total. HG derivatization and SnCl2 reduction (with and without previous oxidation with BrCl) were applied to synthetic and natural (spiked and non-spiked) water samples. The influence of chloride and dissolved organic matter concentrations was studied. The results suggest that the HG procedure is suitable for the simultaneous determination of Hg2+ and MeHg+ in surface water samples. Inorganic mercury analysed by HG (i.e. reducible) is close to the total inorganic mercury.     

Study of the effect of pH, salinity and DOC on fluorescence of synthetic mixtures of freshwater and marine salts

In order to provide support for the discussion of the fate of organic matter in estuaries, a laboratory simulation was performed by changing freshwater ionic strength, pH and organic matter content. The change in spectroscopic characteristics caused by variations in salinity, pH and organic matter concentration in the filtered samples was observed by UV-Vis and fluorescence spectroscopy. The increase in emission fluorescence intensity of dissolved organic matter (DOM) due to increasing salinity (in the range 0 to 5 g l-1) is affected by the pH of the samples. The emission fluorescence intensity at the three maxima observed in the fluorescence spectra, is linearly correlated with dissolved organic carbon (DOC) concentration at several salinity values in the same sample. The increase in organic matter concentration caused a shift in the emission peak wavelength at 410 nm for several salinity values. We concluded that it is necessary to take into account the influence of salinity and pH on emission fluorescence of dissolved organic matter if it is to be used as a tracer in estuarine or near shore areas.     

Assessing the influence of altitude and temperature on biological monitoring of freshwater quality: A preliminary investigation

The effect of altitude and water temperature on biomonitoring of freshwater quality was examined along an unpolluted area (36 km in length) of the upper Río Tajo (central Spain). The macrobenthic and fish communities were studied, and the Biological Monitoring Water Quality (BMWQ) method was applied. As expected, values of altitude and temperature respectively decreased and increased with increasing distance from the river source; these two physical parameters exhibited a negative and significant (P<0.05) correlation coefficient between them. However, despite evident changes in the functional structure of both aquatic communities along the study area, BMWQ scores were similar at all sampling sites. Pearson correlation coefficients between physical and biological parameters were not significant (P>0.05). The BMWQ index only exhibited significant (positive) correlation coefficients with macrobenthic and fish biomasses, indicating that freshwater quality could affect the biological production of fluvial ecosystems. It is concluded that biomonitoring of freshwater quality may be independent of the influence of altitude and water temperature at local spatial scales. Nonetheless, further investigations would be needed to clearly differentiate between the effects of anthropogenic and natural causes on biological monitoring at larger spatial scales.     

Use of in vivo phycocyanin fluorescence to monitor potential microcystin-producing cyanobacterial biovolume in a drinking water source

The source water of a drinking water treatment plant prone to blooms, dominated by potential microcystin-producing cyanobacteria, was monitored for two seasons in 2007-2008. In the 2008 season, the median value for potential microcystin-producing cyanobacterial biovolume was 87% of the total phytoplankton biovolume in the untreated water of the plant. Depth profiles taken above the plant's intake identified three sampling days at high risk for the contamination of the plant's raw water with potentially toxic cyanobacteria. Chlorophyceae and Bacillariophyceae caused false positive values to be generated by the phycocyanin probe when cyanobacteria represented a small fraction of the total phytoplanktonic biovolume present. However, there was little interference with the phycocyanin probe readings by other algal species when potential microcystin-producing cyanobacteria dominated the phytoplankton of the plant's untreated water. A two-tiered method for source water monitoring, using in vivo phycocyanin fluorescence, is proposed based on (1) a significant relationship between in vivo phycocyanin fluorescence and cyanobacterial biovolume and (2) the calculated maximum potential microcystin concentration produced by dominant Microcystis sp. biovolume. This method monitors locally-generated threshold values for cyanobacterial biovolume and microcystin concentrations using in vivo phycocyanin fluorescence.