Utilization of the solid sorbent media in monitoring of airborne cyclophosphamide concentrations and the implications for occupational hygiene

The main objective of the study was to evaluate the applicability of two solid sorbent media (Anasorb 708 and Strata X), the impinger filled with distilled water and PTFE filters for determination of airborne cyclophosphamide (CP) in the hospital working environment. For this purpose, air contamination of Masaryk Memorial Cancer Institute (Czech Republic) was monitored using the sampling apparatus containing the samplers described above. In addition, the surface contamination was also determined using the wipe sampling technique. During the monitoring, contamination of three different workplaces (storage room, preparation room and outpatient clinic) was studied. Using Strata X solid sorbent tubes, airborne CP was determined in all (n = 5) samples collected at the outpatient clinic over a 5 day monitoring period (concentration range: 0.3-4.3 ng m(-3)). Other samplers (including PTFE filters) did not collect any detectable amount of CP (the limit of detection, LOD ≤ 0.1 ng m(-3)). Negative results detected at filter samples indicate that CP determined at Strata X samples was most probably of gaseous origin. Surface contamination ranged from <2 to 19, <8 to 418 and 133-15,500 pg cm(-2) at the storage room, preparation room and outpatient clinic, respectively. The study showed that evaporation of antineoplastic drugs should not be neglected, albeit the concentrations determined in our study are relatively low. Therefore, proper monitoring of airborne contamination should involve simultaneous sampling of both particle-bonded and gaseous phases. In this way, Strata X sorbent tubes seem to be an effective tool for the sampling of gaseous CP in the indoor air.     

Concentrations of cadmium and lead heavy metals in Dardanelles seawater

Cadmium and lead were determined simultaneously in seawater by differential pulse stripping voltammetry (DPSV) preceded by adsoptive collection of complexes with 8-hydroxyquinoline (oxine) on to a hanging mercury drop electrode (HMDE). In preliminary experiments the optimal analytical condition for oxine concentration was found to be 2.10⁻⁵ M, at pH 7.7, the accumulation potential was −1.1 V, and the initial scannig potential was −0.8 V. The peak potentials were found −0.652 V for Cd and −0.463 V for Pb At the 60 s accumalation time. The limit of detection (LOD) and limit of quantitatification (LOQ) were found to be by voltammetry as 0.588 and 1.959 μg l⁻¹ (RSD, 5.50%) for Cd and 0.931 and 3.104 μg l⁻¹ (RSD, 4.10%) for Pb at 60 s stirred accumulation time respectively. In these conditions the most of the seawater samples are amenable for direct voltammetric determination of cadmium and lead using a HMDE. An adsorptive stripping mechanism of the electrode reaction was proposed. For the comparison, seawater samples were also analysed by ICP-atomic emission spectrometry method (ICP-AES). The applied voltammetric technique was validated and good recoveries were obtained.     

Using environmental analytical data to estimate levels of community consumption of illicit drugs and abused pharmaceuticals

A solid phase extraction (SPE) method has been developed and applied in conjunction with a previously reported liquid chromatography tandem mass spectrometry (LC-MS-MS) procedure for the determination of illicit drugs and abused pharmaceuticals in treated wastewater and surface water samples at the ng L(-1) level. A full method validation was also performed and determined levels of analytical sensitivity were found to lie in the 1-10 ng L(-1) range using river water as a test sample matrix and a sample size of 500 mL. The developed procedure was successfully applied for the determination of the chosen analytes in wastewater treatment plants in Dublin, Ireland and rapidly expanding commuter towns in the surrounding counties. Cocaine was detected in 70% of the collected samples in the range of 25-489 ng L(-1), its primary metabolite, benzoylecognine (BZE) was also detected in the range of 22-290 ng L(-1). Other substances detected included morphine, Tempazepam and the primary metabolite of methadone.     

A rapid lateral flow immunoassay for the detection of fungal alpha-amylase at the workplace

Fungal alpha-amylase is a flour supplement which is added to improve the quality of bakery products. Various studies have shown that exposure to this enzyme is an important risk factor for the development of bakers' allergy and this allergy is reported to be one of the most frequent causes of occupational asthma. A rapid assay was developed to monitor exposure to occupational allergens directly at the workplace. The sensitivity of the developed assay is 0.32 ng amylase mL(-1) in a buffer system with the commercially available alpha-amylase preparation Fungamyl 1600S as the standard. Initial validation tests (n = 33) were performed with airborne and settled dust from an industrial bakery. The new lateral flow immunoassay detected amylase in 22 of the 26 samples regarded as positive in an enzyme immunoassay, and was negative for all seven enzyme immunoassay-negative samples, while the four lateral flow immunoassay-negative/enzyme immunoassay-positive samples all had levels below 2 ng mL(-1). The sensitivity of 2 ng mL(-1) of the amylase lateral flow immunoassay is sufficient for first screening purposes and, therefore, this simple and rapid assay may allow direct on-site demonstration of work-related hazards of bio-allergen exposure. This would be particularly useful in occupational hygiene practice, especially in traditional or small-scale bakeries which lack the technological skills for testing the exposure to respiratory allergens.     

Is PM10 mass measurement a reliable index for air quality assessment? An environmental study in a geographical area of north-eastern Italy

The aim of this study was to measure the concentration of some metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Ti) in PM(10) samples collected in one urban and one industrial site and to assess that PM(10) total mass measurement may be not sufficient as air quality index due to its complex composition. Metals were determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and differential pulsed anodic stripping voltammetry (DPASV). The measured concentrations were used to calculate the content of metals in the PM(10) total mass, and to estimate the enrichment factors and the correlations between PM(10), metal concentrations and meteorological data for the two sites. The mean PM10 concentration during the sampling period in the urban site exceeded the annual European Union (EU) standard (40 microg/m(3)) and, for some sampling days, the daily EU standard (50 microg/m(3)) was also exceeded. In opposite, both EU standards were never exceeded in the industrial site. The overall metal content was nearly double in the industrial site compared to the urban one, and the mean Ni concentration exceeded the EU annual limit value (10 ng/m(3)). The metals with the highest enrichment factor were Cd, Cu, Ni and Pb for both sites, suggesting a dominant anthropogenic source for these metals. Metal concentrations were very low and typical of rural background during Christmas holidays, when factories were closed. PM(10) total mass measurement is not a sufficient air quality index since the metal content of PM(10) is not related to its total mass, especially in sites with industrial activities. This measurement should be associated with the analysis of toxic metals.     

Determination of CH4, CO2 and N2O in air samples and soil atmosphere by gas chromatography mass spectrometry, GC-MS

A method for determination of the climate gases CH4, CO2 and N2O in air samples and soil atmosphere was developed using GC-MS. The method uses straightforward gas chromatography (separation of the gases) with a mass spectrometric detector in single ion mode (specific determination). The gases were determined with high sensitivity and high sample throughput (18 samples h(-1)). The LOD (3sigma) for the gases were 0.10 micro L L(-1) for CH4, 20 microL L(-1) for CO2 and 0.02 microL L(-1) for N2O. The linear range (R2 = 0.999) was up to 500 microL L(-1) for CH4, 4000 microL L(-1) for CO2 and 80 microL L(-1) for N2O. The samples were collected in 10 mL vials and a 5 microL aliquot was injected on column. The method was tested against certified gas references, the analytical data gave an accuracy within +/-5% and a precision of +/-3%. The presence of < or = 10% by volume of C2H2 (often used experimentally to prevent N2 formation from N2O) did not interfere with detection for the targeted trace gases.     

长江南京段新兴污染物污染特征及风险评估

在长江南京段上游至下游依次布设6个采样点采集水样,使用固相萃取和LC-MS/MS相结合的方法对5种选定药物的质量浓度进行测定,并采用风险熵模型评估其生态风险。结果表明,6个采样点均检测到药物存在。其中,四环素、红霉素、罗红霉素和氯霉素的检出率为100%,最高检出值为10.29 ng/L(氯霉素)。与国内外其他地表水相比,长江南京段水中的药物质量浓度较低。生态风险评估结果表明,长江南京段水中5种药物的风险熵值均低于1,对水生生物不存在高风险。     

Monitoring trace metals in urban aerosols from Buenos Aires city. Determination by plasma-based techniques

A study was undertaken, within the framework of a 3 years national project, to assess the content of 13 elements in airborne particulate matter collected in representative zones of the metropolitan area of Buenos Aires. The sampling strategy followed consisted in collecting simultaneously 67 samples of PM10 particulate matter in 9 sampling sites covering an area of about 30 km2 during one week. The collection was performed on ash-free fibre-glass filters using high volume samplers. A combination of aqua regia and perchloric acid was used for leaching metals from filters. Key elements, namely Al, Ca, Cu, Fe, Mn, Mo, Ni, Pb, S, Sb, Sn, Zn and Zr, were determined by inductively coupled plasma-optical emission spectrometry (ICP-OES) and inductively coupled plasma-mass spectrometry (ICP-MS) at micro g g(-1) and ng g(-1) levels. Analyte concentration varied from 130 ng g(-1)(Mo) to over 30%(Ca). Multivariate statistical analysis was performed on the data set including the measured elemental compositions for the monitored period. The atmospheric concentration found for Pb confirms the decreasing levels of this element since the introduction of unleaded gasoline in 1995: 88 ng m(-3)(2001) < 220 ng m(-3)(1997) < 3900 ng m(-3)(1994). The average S concentration above 3 microg m(-3) is somehow unexpectedly high for Buenos Aires since the relatively low S content of liquid fuels and the massive usage of natural gas imply low emissions of this element from combustion activities. To the best of our knowledge, S concentrations are reported for the first time for this city.     

Exposure assessment in Beijing, China: biological agents, ultrafine particles, and lead

In this study, air samples were taken using a BioSampler and gelatin filters from six sites in Beijing: office, hospital, student dormitory, train station, subway, and a commercial street. Dust samples were also collected using a surface sampler from the same environments. Limulus amoebocyte lysate (LAL) and Glucatell assays were used to quantify sample endotoxin and (1,3)- ${\rm{\beta}} $ -d-glucan concentration levels, respectively. Enzyme-linked immunosorbent assay (ELISA) was used to measure the dust mite allergens (Der p 1 and Der f 1). Ultrafine particle and lead concentrations in these sampling sites were also measured using P-Trak and atomic absorption spectrometer, respectively. Analysis of variance (ANOVA) and linear regression analysis were used to analyze the concentration data. Higher culturable bacteria (12,639 CFU/m³) and fungi (1,806 CFU/m³) concentrations were observed for the train station and the subway system, respectively. For the rest of sampling sites, their concentrations were comparable to those found in western countries, ranging from 990 to 2,276 CFU/m³ for bacteria, and from 119 to 269 CFU/m³ for fungi. ANOVA analysis indicated that there were statistically significant differences between the culturable bacterial and fungal concentration levels obtained for different sites (p value = 0.0001 and 0.0047). As for dust allergens, endotoxin, and (1,3)-β -d-glucan, their concentrations also seemed to be comparable to those found in the developed countries. Airborne allergen concentrations ranged from 16 to 68 ng/m³. The dust-borne allergen concentration was observed to range from 0.063 to 0.327 ng/mg. As for endotoxin, the highest airborne concentration of 25.24 ng/m³ was observed for the commercial street, and others ranged from 0.0427 to 0.1259 ng/m³. And dust-borne endotoxin concentration ranged from 58.83 to 6,427.4 ng/mg. For (1,3)-β -d-glucan, the airborne concentration ranged from 0.02 to 1.2 ng/m³. Linear regression analyses showed that there existed poor correlations between those in airborne and dust-borne states (R²?=?0.002~0.43). In our study, the lowest ultrafine particle concentration about 5,203 pt/cm³ was observed in office and the highest was observed at the train station, up to 32,783 pt/cm³. Lead concentration was shown to range from 80 to 170 ng/mg with the highest also observed at the train station. The information provided in this work can be used to learn the general situation of relevant health risks in Beijing. And the results here suggested that when characterizing exposure both airborne and dust-borne as well as the environments should be considered.     

Optimisation and application of the voltammetric technique for speciation of chromium in the Patos Lagoon Estuary—Brazil

The chemical speciation analysis of chromium in one of the most important South American Estuary was performed for the first time. Samples were collected in Patos Lagoon Estuary (Brazil) and were analysed by adsorptive cathodic stripping voltammetry, with the following analytical figures of merit: limit of detection, 0.1 nmol L(-1); precision RSD?=?3%, n?=?7; linearity, from limit of quantitation up to 20 nmol L(-1); and accuracy of 99.8%, expressed as recovery. No labile chromium forms were identified in samples, beside industries and a city were near the study area. It is pointed out a reverse correlation between total and non-active chromium and salinity, which could be explained by biogeochemical processes.     

An assessment of tree health and trace element accumulation near a coal-fired generating station, Manitoba, Canada

A forest health assessment was performed in stands dominated by bur oak and trembling aspen to study the potential effects of airborne emissions from a 132 MW coal-fired station. Forty-two stands were sampled within a 16-km radius of the station for both foliar stress symptoms and trace element toxicology. The concentrations of tracer elements (As, Ba, Sr, and V) in the leaf litter were not spatially congruent with airborne emission deposition models (except Ba, which showed elevated levels immediately SE of the station), nor were they at phytotoxic levels. Elemental concentrations were significantly related to soil parameters including organic matter and texture. No patterns were found in forest health along directional or distance gradients from the generating station. Trembling aspen stands demonstrated little decline in general, but three of the 19 bur oak plots, all located on thin sandy soils developed on calcareous till, demonstrated branch dieback. In addition to poor soil conditions, two of these sites also had high water tables, and exhibited tree mortality. The bur oak decline did not appear to be related to emissions from the station, but is suspected to be a result of poor site quality, with urban development as a confounding factor.     

Platinum concentrations in Danish air samples determined by instrumental neutron activation analysis

Platinum, gold and calcium concentrations of 20 samples of airborne dust collected at two sampling sites between 1995 and 1997 in the city of Copenhagen, which suffers from heavy traffic, were determined by instrumental neutron activation analysis (INAA). INAA of platinum using the 199Au daughter of 199Pt was performed. Two interferences on the INAA of platinum were removed by calculations. The spectral interference on 199Au from the 47Sc daughter of 47Ca was removed by separating the 157-161 keV doublet peak into its components by calculating the counts due to 47Sc from the counts of the parent 47Ca. The contribution of 197Au to 199Au by two neutron absorption was corrected for using the ratio 198Au/199Au in a pure Au standard. From the INAA results, high platinum concentrations are present in air in the range 0.25-2.74 ng m-3 and gold concentrations in the range 0.10-1.96 ng m-3.     

Determination of atrazine in surface waters by combination of POCIS passive sampling and ELISA detection

Polar organic compound integrative samplers (POCIS) in combination with instrumental techniques such as LC-MS-MS were previously used to monitor environmental pollutants but the performance of alternative immunochemical methods such as ELISA (enzyme-linked immunosorbent assay) has been explored less. In the present study, POCIS technology was applied to surface water sampling in the Czech Republic, and ELISA was used as a detection technique for the herbicide atrazine. In the first study, 28 samples from streams around small municipal waste water treatment plants (WWTPs) were collected using two different devices (POCISpest and POCISpharm) over the course of 21 days. Elevated atrazine concentrations (up to 25 ng per POCIS) were found in samples down-stream of WWTPs. This observation was also confirmed in another two year study (4 sampling periods) investigating 7 river sites around a major city of Brno as well as the inlet and outlet of the city's WWTP. High atrazine levels were systematically determined at the outlet from the WWTPs (120-605 ng per POCIS). A decreasing trend in the atrazine concentrations in rivers around the city of Brno has been observed, with the highest levels observed within the first sampling period in spring 2007 (100-600 ng per POCIS, with an extreme value of 2760 ng per POCIS). Results of the atrazine ELISA were closely correlated with LC-MS/MS, which confirmed good applicability of ELISA as a cost-effective screening tool.     

A near real-time system for continuously monitoring airborne subtilisin-type enzymes in the industrial atmosphere

We describe the development and validation of a portable system comprising an air sampler coupled to an automated flow injection analysis device. The system is able to monitor airborne concentrations of subtilisin-type enzymes in the workplace atmosphere on a continuous basis. Sampling is in two stages: using a sampling head that is designed to mimic human respiration at approx. 1 m s(-1) at a sampling rate of 600 l min(-1). In the second stage, the captured particles are deposited by impaction from the air stream onto the inner surface of a cyclone that is continuously washed with a jet of buffer solution. Deposited particles are then washed into a reservoir from which samples are taken every 5-6 min and injected automatically into a continuous flow injection analysis system. Proteolytic enzyme in the sample passes through a bioreactor maintained at about 40 degrees C. This contains a cellulose solid phase matrix on which is covalently immobilised Texas Red-labelled gelatin as substrate. The passing enzyme partially digests the substrate releasing fluorophore that is detected down stream in a flow cell coupled to a fluorimeter. The system is calibrated using enzyme standards and the intensity of the resulting peaks from the ex-air samples is converted to airborne concentrations using a mathematical model programmed into a PC. The system has a limit of detection of 4.8 ng m(-3) and a dynamic range of 5-60 ng m(-3). The within assay precision (RSD) is 6.3-9.6% over this range. The within batch precision is 20.3% at 20 ng m(-3) and the corresponding between batch value is 19.5%. The system has been run for periods up to 8 h in the laboratory and for up to 4 h at a factory site and the values obtained compared with time-averaged values obtained from a conventional Galley sampler and in-house analysis when reasonable agreement of the results was observed. The stability of the system over 21 days of continuous use with standards injected periodically was studied. Linearity was observed for all the standard plots throughout. At the end of 21 days, after a total exposure equivalent to 2395 ng ml(-1) of Savinase, the signal due to the 5.0 ng ml(-1) standard was still easily detectable.     

Fractionation of eleven elements by chemical bonding from airborne particulate matter collected in an industrial city in Argentina

A four-step chemical sequential extraction procedure was used to evaluate the distribution of Al, As, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn in airborne particulate matter collected on glass fibre filters using a high-volume sampler. Two sets of samples were collected in 2001 (winter and summer campaigns) in representative zones of an industrial city of Argentina. The leaching scheme was applied to PM-10 particles and consisted in extracting the elements in four fractions, namely soluble and exchangeable elements; carbonates, oxides and reducible elements; bound to organic matter and sulfidic metals; and residual elements. Metals and metalloids at microg g(-1) level were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). Analyte concentration varied from 14 microg g(-1) (equivalent to 1.0 ng m(-3)) for As to 11.8 mg g(-1) (equivalent to 2,089 ng m(-3)) for Al. Seven elements, namely Al, Cr, Fe, Mn, Pb, Ti and Zn showed similar distributions in both seasons while As was distributed in a significantly different manner in each season. The results exhibited low As contents in the first and second fractions that could be associated with routine coal combustion and a high content in the third and fourth fractions of the summer samples that could be linked to the use of pesticides. Aluminium, As, Cu, Mn, Ni, Ti, V and Zn were found in different percentages in the more bioavailable aqueous fraction with As, Mn, V and Zn exhibiting solubilities greater than 1% while Cr and Pb being insoluble. The content of Al, Cr, Cu, Fe, Ni, Pb, and Zn in the residual fraction was, in average, higher than 50%. A comparative assessment of the use of the underlying information available from fractionation studies compared to that obtained from total element content was done for Fe and Mn. It showed that the results obtained using chemical sequential extraction procedures allowed further discrimination of the potential air pollution sources.     

On-line solid phase extraction and liquid chromatography/tandem mass spectrometry to quantify pharmaceuticals, pesticides and some metabolites in wastewaters, drinking, and surface waters

A simple on-line method was developed for the analysis of pharmaceuticals, pesticides and some metabolites in drinking, surface and wastewater samples. The technique is based on the use of on-line solid-phase extraction combined with liquid chromatography electrospray tandem mass spectrometry with positive electrospray ionization (LC-ESI(PI)-MS/MS). The injection of only 1 mL of filtered water sample is used with a total analysis time of 20 min, including the period required to flush the SPE cartridge with organic solvent and reconditioning the LC column. Method detection limits were in the range of 2 to 24 ng L(-1) for the compounds of interest, with recoveries from 87 to 110% in surface as well as wastewater samples. Matrix effects were observed for some compounds without exceeding more than 25%. All results displayed a good degree of reproducibility, with relative standard deviations (RSD) of less than 12% for all compounds. Moreover, at least 200 samples were analyzed without altering the performance of the pre-concentration column. This method was preferred over traditional off-line procedures because it minimizes tedious sample preparation, increases productivity and sample throughput. The analysis of various water and wastewater samples showed that caffeine, carbamazepine and atrazine could be detected in all the samples analysed and the selected compounds are always present in at least one of the sample types.     

POCIS sampling in combination with ELISA: screening of sulfonamide residues in surface and waste waters

Sulfonamide antibiotics coming from both human and veterinary medicine are among the most common emerging pollutants in freshwater. The present paper shows the successful application of passive sampling using POCIS in combination with an immunochemical ELISA technique and HPLC/MS/MS analysis to study the distribution of sulfonamides in streams around small towns in the Czech Republic, as well as around a major agglomeration of the city of Brno, including its waste water treatment plant (WWTP). Results indicated the presence of sulfonamides at most studied sites with concentrations ranging from <20 up to 736 ng of sulfamethoxazole equivalents per POCIS. Very high levels were detected in both the influent and effluent of the Brno WWTP with maxima > 8000 ng SMX per POCIS. All samplers collected down-stream of the studied towns and WWTPs clearly showed an increase in sulfonamide drug residues. Higher concentrations were determined in rivers at the city of Brno agglomeration. In agreement with other available studies, these findings indicate low efficiency of conventional WWTPs to eliminate polar pharmaceuticals such as sulfonamides. Good performance and correlation with the LC/MS results, as well as ease of use, indicate good potential for the immunochemical ELISA technique to become the screening tool for sulfonamide determination in surface waters including passive samplers.     

Development of a calibration system to evaluate VOC losses in a branch enclosure

Considerable uncertainties are associated with the experimental estimates of emission rates of different volatile organic compound (VOC) species from the biosphere to the atmosphere. Some of this uncertainty derives from the sampling and analytical procedures used in emission rate measurements. A calibration system was developed in order to evaluate possible errors in the measurements of biogenic emission rates using a branch enclosure system. Two types of calibration procedures were tested, a standard additions technique and an internal standard procedure. Both techniques were used to evaluate possible losses while sampling isoprene and monoterpenes, which are the most abundant VOCs of biogenic origin. The losses to Teflon lines and the empty sampling system were tested and losses to the branch enclosure system installed on two VOC emitting plant species were evaluated. A considerable loss of isoprene (approximately 18% of inflow concentration 65 ng l(-1)) to the empty enclosure system and to the system installed on the plant was measured, but no losses of monoterpenes were observed.     

Evaluation of the Operational Street Pollution Model Using Data from European Cities

This paper presents a sensitivity analysis and an evaluation of the semi-empirical model known as Operational Street Pollution Model (OSPM). The model is capable of calculating airborne concentrations of exhaust gases emitted by vehicles, within a street canyon. OSPM has been extensively evaluated using data collected over a two year period (1994–1995), during a monitoring campaign carried out in Jagtvej, Denmark. Further evaluation of the model was carried out using data collected in Göttinger Strasse, Hannover (1994) and Schildhorn Strasse, Berlin (1995), both in Germany. In all cases, model runs were carried out for carbon monoxide.Two sets of emission factors were used for the two street canyons in Germany; namely that available within OSPM and another separate set of emission factors derived from data collected in Germany. In the calculation of the latter set, the urban driving patterns and variations in the vehicle fleet composition according to the engine capacity were assumed accordingly. A correlation coefficient of 0.90 between the modelled and measured concentrations was obtained for all the cases considered when using the emission factors of OSPM. A correlation coefficient of about 0.85 was obtained with the newly proposed emission factors when applied to Göttinger and Schildhorn Strasse.