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In situ gamma-ray spectrometry for environmental monitoring: a semi empirical calibration method.

In situ gamma spectrometry using high-purity germanium (HPGe) detectors is a frequently used method for the determination of radionuclide ground deposition levels. Such measurements do, however, require an efficiency calibration based on detector sensitivity and parameters such as soil density and vertical activity distribution. In this work, a novel expression is used for the detector efficiency, incorporating both the influence of photon energy and incidence angle. Detector-specific efficiency data are determined empirically. For the theoretical calculation of the photon fluence at the detector, a three-layer model of finite thickness is developed for the description of soil density and vertical activity distribution. In order to facilitate the calibration of in situ measurements, a PC program has been developed to enable rapid, on-site calculations of radionuclide ground deposition levels. The semi empirical calibration method was tested on in situ measurements with two different detectors, and the results show good agreement with results obtained from traditional soil sampling.

Calibration↗

Biological and environmental monitoring of occupational exposure of pharmaceutical plant workers to methotrexate.

The exposure of 11 pharmaceutical plant workers to methotrexate (MTX) was studied. Personal air samples were taken during the different manufacturing processes: drug compounding, vial filling, and tablet preparation. The uptake of MTX was established by the determination of MTX in urine. MTX was analyzed using the fluorescence polarization immunoassay (FPIA), a method that is frequently used for monitoring serum levels in patients treated with MTX. The FPIA method was modified in such a way that MTX could be measured quickly and efficiently in air and urine samples. MTX was detected in air samples of all workers except for those involved in the vial filling process (range: 0.8-182 micrograms/m3; median: 10 micrograms/m3). The highest concentrations were observed for workers weighing MTX (118 and 182 micrograms/m3). MTX was detected in urine samples of all workers. The mean cumulative MTX excretion over 72-96 h was 13.4 micrograms MTX-equivalents (range: 6.1-24 micrograms MTX-equivalents). A significantly lower background level of 10.2 micrograms MTX-equivalents was measured in urine of 30 control persons (range: 4.9-21 micrograms MTX-equivalents).

Adult↗

A three-microphone system for real-time directional analysis: toward a device for environmental monitoring in deaf-blind.

Sound localization is a problem for the hearing impaired, deaf, and deaf-blind. A laboratory prototype of a three-microphone digital system for real-time directional analysis of sound sources that is mounted on eyeglasses has been developed. A cross-correlation algorithm is used for determinations of time and phase differences between the three microphone signals. The equipment was evaluated in a sound-treated test room with noise and speech stimuli from 12 different directions. It has an adequate precision (within approximately +/- 10 degrees) for speech and noise bursts in the frequency range 0.5-4 kHz, and for testing with words in a sound field the error percentage is very close to 0 at 0-degrees azimuth. The robustness of the algorithm in terms of signal-to-noise ratio is documented and reaches about +8 dB in different directions for speech and up to 0 dB for noise bursts. It is concluded that the construction of a robust system for directional analysis with sufficient efficiency for further experiments has been achieved.

Algorithms↗

Environmental monitoring of fluoride emissions using precipitation, dust, plant and soil samples.

A pollution gradient was observed in precipitation, plants and soils sampled at different locations around a fluoride producing chemical plant in Germany. In all samples the influence of emissions was discernible up to a distance of 500 m from the plant. However, fluoride concentrations in plant bioindicators (leaves of birch and black berry) and in bulk precipitation showed a more pronounced relationship with the distance from the source than fluoride concentrations in soil. Vegetables sampled in the vicinity of the plant also had elevated concentrations of fluoride, but only the consumption of larger quantities of this material would lead to exceedances of recommended daily F-intake. The present study did not indicate the existence of low phytotoxicity thresholds for fluoride in the plant species used in the study. Even at very high fluoride concentrations in leaf tissue (963 ppm) plants did not show injury due to HF. Dust sampling downwind of the chemical plant confirmed that particulate fluoride was of minor importance in the study area.

Air Pollutants↗

Power analysis and practical strategies for environmental monitoring.

What sample size n is needed to have 1 - beta chance of detecting a magnitude delta response to pollution impact? A design where the same sites are sampled both before and after impact is more efficient than a design where sites are reallocated for the after-impact sampling. Taylor's Power Law can be used to estimate the n necessary to achieve specified power for a wide range of variance-mean relationships. Solutions can easily be obtained where the error coefficient of variation and the percentage change due to impact are of interest rather than the error standard deviation and absolute change. Estimation of the n necessary to detect a hypothesized multivariate response can easily be done. When p response variables are uncorrelated and all respond equally to impact, the required n is approximately the same as for a univariate test using one of the variables. If only one of the p variables responds, n is approximately p times that number. However, if the variables are correlated and the vector of response differs from the natural variation, then the required sample size is smaller. In this circumstance the multivariate test can be very powerful.

Environmental Monitoring↗

[Environmental monitoring and biological monitoring of young people exposed to nonoccupational levels of formaldehyde, toluene and other hydrocarbons].

During the period of 1983-1985, in two of apprentice schools of P. town the health disorders were investigated in the total of 82 apprentices 15-18 years old from the environment with elevated concentrations of formaldehyde and toluene. The study was contrasted with a control total of 42 apprentices. Cytogenetical examination has been performed, and selected immunological parameters in both blood serum and saliva have been assessed with red and white blood cells counts including differential formula of white blood cells. In addition, the atmospheric toxicity of formaldehyde and vapours of organic solvents (toluene, xylene, varnish naphtha) was measured. A single biological exposure test has been performed for the detection toluene. Statistically significant were differences in occurrence of cell chromosomal aberrations between the group of long term formaldehyde and toluene exposure (averagely 3.53% ABB) and controls (2.21% ABB) as obtained in 1983 and 1984, and so were differences between the long term-to-toluene exposed group (3.30% ABB) and the above mentioned control group as obtained in 1984. No similar results were stated between the long term-to-formaldehyde exposed (3.07% ABB) and control (2.55% ABB) groups in 1985. The main evidence consisted in finding the genotoxical/clastogenic effect of observed agents associated with mainly chromosomal abnormalities of chromatide type. It outflowed from the determination of selected serum proteins (Ig and acute phase proteins) and salivary lysozyme that the group under the combined influence of formaldehyde and toluene showed significantly lower IgG and higher alpha-1-antitrypsin (A1AT). The group at risk of toluene was characteristical in elevated concentrations of alpha-2-macroglobulin (A2M) and A1AT. Most pronounced changes in first year had been revealed through the evaluation of the influence of the duration at risk (significant decrease in IgA and prealbumin, and the increase in A2M and A1AT). The infectious disease as experienced 2 month prior the collection resulted in a significant decrease of IgM, A2M and A1AT in risky groups in individuals with infection in anamnesis. Salivary lysozyme concentration of apprentice environmentally exposed to formaldehyde in the noon showed the decrease, whereas its increase occurred in controls with the difference on 5% significancy level. Blood count assessements showed no significant differences between the investigated values as well as any were assessed between the incidence of health disorders of apprentices and their correspondance to the given group.

Adolescent↗

A gas-phase biosensor for environmental monitoring of formic acid: laboratory and field validation.

In order to encourage more exposure measurements to be performed, a formic acid gas-phase biosensor has been developed for this purpose. In the present paper, an enzyme based biosensor has been validated with respect to analyte selectivity and on-site use. To ensure that the sampler developed measures the compound of interest the biosensor was exposed to three near structural homologues to formic acid, i.e. acetic acid, methanol and formaldehyde. These vapours were generated with and without formic acid and the only compound that was found to have an effect on the performance of the biosensor, albeit a small one, was acetic acid. The field test was performed in a factory using formic acid-containing glue for glulam products. In parallel to the measurements with the biosensor a well defined reference method was used for sampling and analysing formic acid. It was found that the biosensor worked satisfactorily in this environment when used in a stationary position. It was also shown that the biosensor could determine formic acid vapour concentrations down to 0.03 mg m(-3).

Biological Assay↗

Environmental monitoring of nitrous oxide during dental anaesthesia.

AIM: The study was carried out to see if levels of nitrous oxide in dental theatres and community dental clinics were being controlled in accordance with the Control of Substances Hazardous to Health Regulations. SETTING: A multi-centre study looked at exposure levels in a dental teaching hospital and two community dental clinics in the South Wales area between 1997 and 1998. METHODS: A MIRAN infra-red spectrophotometer was used to measure static levels of nitrous oxide during general anaesthesia and conscious sedation. NIOSH method 6600 was used to collect personal samples of the individual administering the anaesthetic. RESULTS: The results showed compliance with the regulations when averaged out over an 8 hour time weighted average. However, over short periods of time peak concentrations of up to 1190 ppm were observed through static sampling, and up to 734 ppm through personal sampling. CONCLUSIONS: The results highlighted the need to provide adequate control measures such as anaesthetic gas scavenging, to reduce occupational exposure to dental staff in dental operating theatres and community dental clinics, therefore providing a safe working environment.

Air Pollutants, Occupational↗

Time series of long-term annual fluxes in the streamwater of nine forest catchments from the Swedish environmental monitoring program (PMK 5).

International cooperation has contributed to major declines in SO(2) emission and S deposition during the last two decades in Europe. The chemical recovery from already anthropogenically acidified sites however, has been slow. In the present paper, long-term trends of chemical fluxes from nine selected forested reference catchments were studied, to detect recovery from acidification and leaching of S and base cations (BC). A decline in S deposition resulted in a decreased flux of non-marine sulfate (SO(4)*) in seven of nine streams, with statistically significant changes in four. The two cases with slight increases in SO(4)* flux resulted from increasing water flow. The SO(4)* decrease was followed by a recovery from acidification in terms of increased ANC flux in those sites in southern Sweden that were chronically acidified. The recovery was probably slowed down by leaching of SO(4) from the soil and a decrease in the flux of BC. A better understanding of the processes for leaching of SO(4) and BC is needed in order to quantify the need for further restrictions of sulfur emissions to allow a long term recovery of acidified catchments. The flux calculations available from small catchments such as those in this study, are of value for that understanding.

Acid Rain↗

Temperature-electrical conductivity relation of water for environmental monitoring and geophysical data inversion.

Electrical conductivity (EC) is widely used for monitoring the mixing of fresh water and saline water, separating stream hydrographs, and geophysical mapping of contaminated groundwater. The measured EC values at various temperatures need to be reported as corresponding to a standard temperature because EC is dependent on temperature. An arbitrary constant is commonly used for temperature compensation assuming that EC-temperature relation is linear (for example 2% increase of EC per 1 degrees C). This paper examines the EC-temperature relation of natural waters having vastly different compositions and salinities. EC-temperature relation was slightly nonlinear in a temperature range 0-30 degrees C, but the linear equation approximated the relation reasonably well. The temperature compensation factor corresponding to 25 degrees C ranged between 0.0175 and 0.0198. When the mean value 0.0187 was used, the error of estimating EC at 25 degrees C from EC at 10 degrees C was less than about 2% for all samples tested. Temperature compensation factors vary substantially depending on the choice of standard temperature. Therefore, a care must be taken when standard temperatures different from 25 degrees C are used.

Calibration↗

Environmental monitoring of carbaryl applied in urban areas to control the glassy-winged sharpshooter in California.

Carbaryl insecticide was applied by ground spray to plants in urban areas to control a serious insect pest the glassy-winged sharpshooter, Homalodisca coagulata (Say), newly introduced in California. To assure there are no adverse impacts to human health and the environment from the carbaryl applications, carbaryl was monitored in tank mixtures, air, surface water, foliage and backyard fruits and vegetables. Results from the five urban areas - Porterville, Fresno, Rancho Cordova, Brentwood and Chico - showed there were no significant human exposures or impacts on the environment. Spray tank concentrations ranged from 0.1-0.32%. Carbaryl concentrations in air ranged from none detected to 1.12 microg m(-3), well below the interim health screening level in air of 51.7 microg m(-3). There were three detections of carbaryl in surface water near application sites: 0.125 ppb (parts per billion) from a water treatment basin; 6.94 ppb from a gold fish pond; and 1737 ppb in a rain runoff sample collected from a drain adjacent to a sprayed site. The foliar dislodgeable residues ranged from 1.54-7.12 microg cm(-2), comparable to levels reported for safe reentry of 2.4 to 5.6 microg cm(-2) for citrus. Carbaryl concentrations in fruits and vegetables ranged from no detectable amounts to 7.56 ppm, which were below the U.S. EPA tolerance, allowable residue of 10 ppm.

Air Pollutants↗

Application of a cytochrome P-450 IA1-ELISA in environmental monitoring and toxicological testing of fish.

1. An enzyme-linked immunosorbent assay (ELISA) based on polyclonal rabbit anti-cod cytochrome P-450 IA1 IgG has been developed in our laboratory. 2. The antibodies employed in the ELISA demonstrate good cross-reactivity with the homologous protein in a number of other fish species, giving cross-reacting protein bands o 54-59 kDa in liver microsomes, as determined by Western blotting. 3. The ELISA technique has been used in numerous experiments with both field collected and laboratory exposed fish of different species, showing good correlation with contaminant exposure. 4. In some instances of PCB exposure where the classical P-450 IA1 monooxygenase assay 7-ethoxyresorufin O-deethylase (EROD) failed to reveal any induction, the ELISA technique demonstrated increased levels of P-450 IA1 protein, indicating inhibiting effects of the PCBs on EROD measurement. 5. In tissues like gill filaments, and in whole cod larvae, where EROD activity is barely detectable, if at all, the ELISA technique showed induction after exposure to a water soluble fraction (WSF) of North Sea crude oil. 6. The results reviewed indicate the usefulness of the ELISA technique to allow rapid screening of a large number of samples, and especially when catalytic measurement is difficult or impossible due to (a) small sample or tissue size, (b) loss of activities in bad storage conditions, or (c) presence of compounds inhibiting activity.

Animals↗

Environmental monitoring: correlating air measurements of substances with immune response.

In summary, data from animal models would suggest that air measurements of substances can be correlated with immune response, be it immunodepression or either of the two forms of immunostimulation-autoantibody formation or specific immunologic sensitization. However, became immunodepression and autoantibody formation are not specific for a given substance, and because they can be induced by a variety of other factors such as drugs and intercurrent viral infections, it would seem unlikely that correlations between air measurements and measurements of immunodepression or autoantibody formation could be very useful. In contrast, specific immunologic sensitization is a response that can only be induced by exposure to a specific agent. The major problem confronting investigators attempting to perform concentration-response studies in humans is accurate measurement of workplace exposures. If exposures could be reliably quantified, it is likely that concentration-response correlations could be determined for worker groups. This could prove useful for estimating exposure of groups based on aggregate immune response. It would be most useful, however, for determining threshold concentrations below which a very low proportion of workers--perhaps 1 in 100 or even 1 in 1000--would become sensitized. These threshold concentration levels of sensitizing substances could be used to develop permissible exposure levels in the workplace. Reducing workplace sensitization and diseases such as occupational asthma and hypersensitivity pneumonitis would be of obvious benefit to workers, management, government, and society at large.

Air Pollutants, Occupational↗

Environmental monitoring of historical change in arsenic deposition with tree bark pockets.

ICP-MS analysis recorded historical change (c. 1846 to 2002) in the arsenic concentration of bark included within the trunks (tree bark pockets) of two Japanese oak trees (Quercus crispula), collected at an elevated location approximately 10 km from the Ashio copper mine and smelter, Japan. The arsenic concentration of the bark pockets was 0.016 +/- 0.003 microg cm(-2) c. 1846 (n = 5) and rose 50-fold from c. 1875 to c. 1925, from approximately 0.01 to 0.5 microg cm(-2). The rise coincided with increased copper production in Ashio from local sulfide ores, from 46 tons per year in 1877 to 16,500 tons per year in 1929. Following a decline in arsenic concentration and copper production, in particular during the Second World War, a second peak was observed c. 1970, corresponding to high levels of production from both local (6,000 tons per year) and imported (30,000 tons per year) ores, smelted from 1954. Compared to the local ores, the contribution of arsenic from imported ores appeared relatively low. Arsenic concentrations declined from c. 1970 to the present following the closure of the mine in 1974 and smelter in 1989, recording 0.058 +/- 0.040 microg cm(-2) arsenic (n = 5) in surface bark collected in 2002. The coincident trends in arsenic concentration and copper production indicated that the bark pockets provided an effective record of historical change in atmospheric arsenic deposition.

Air Pollutants↗

A fluorescence-based sensing system for the environmental monitoring of nickel using the nickel binding protein from Escherichia coli.

A sensing system for nickel based on the nickel binding protein (NBP) from Escherichia coli is shown to be feasible. The versatility of NBP was demonstrated by its use in three different assay formats. When the NBP binds nickel, it undergoes a conformational change that can be used as the basis for an optical sensing system for nickel. The NBP gene was overexpressed in E. coli and the protein purified in a single step using perfusion anion-exchange chromatography. A unique cysteine residue at position 15 in the NBP was labeled with the fluorophore, N-[2-(1-maleimidyl)ethyl]-7-(diethylamino)coumarin-3-carboxamide (MDCC). In a spectrofluorimetric assay, there was a maximum of 65% quenching of the fluorescence signal produced by NBP-MDCC in the presence of nickel. A response curve for nickel using NBP-MDCC revealed a detection limit of 8 x 10(-8) mol L(-1). NBP-MDCC was also used to develop assays in microtiter plate and fiber optic bundle formats. Detection limits for nickel using these formats were also in the submicromolar range. Selectivity studies conducted with other divalent metals, including copper, cobalt, iron, cadmium, and manganese, showed that fluorescence quenching for cobalt was similar in magnitude but with a detection limit more than 10-fold higher than for nickel. The quenching responses were lower for the other metals, with detection limits at least 10 to 100 times higher than for nickel. These results suggest that fluorescently labeled NBP is potentially useful in the development of a sensing system for nickel.

Bacterial Proteins↗

Miniaturized redox potential probe for in situ environmental monitoring.

The need for accurate, robust in situ microscale monitoring of oxidation-reduction potentials (ORP) is required for continuous soil pore water quality monitoring. We are developing a suite of self-contained microelectrodes that can be used in the environment, such as at Superfund sites, to monitor ORP in contaminated soils and sediments. This paper presents details on our development of microelectrode sensor arrays for ORP measurements. The electrochemical performance of these ORP electrodes was fully characterized by measuring redox potentials in standard solutions. It found that the newly developed integrated ORP microelectrodes produced a very stable voltage response (the corresponding rate of the integrated microelectrode potential change was in the range of 0.6-1.1 mV/min), even when the measurement was carried out outside of a Faraday cage where signals from most conventional microelectrodes are usually inhibited by external electrical nose. These new microelectrodes were easier to fabricate and were more robust than conventional microelectrodes. The tip size of the integrated ORP microelectrode was approximately 200 nm square, with a taper angle of approximately 20 degrees and a length of 57 microm. The integrated ORP microelectrode exhibited better signal stability and substantially shorter response times (from less than a few milliseconds to 30 s, depending on the standard solution used) than the commercial millielectrode (a few minutes). Compared with the slope of the commercial millelectrode, the slope of the integrated microelectrode (61.5 mV/pH) was closerto the ideal slope against quinhydrone calibration solutions. Therefore, it is to be expected that the newly developed ORP microelectrode may have wider applications in contaminated soils, biofilms, and sediments.

Electrochemistry↗

Environmental monitoring in the vicinity of the Mayak atomic facility.

The goal of radiation monitoring in the zone influenced by the operation of the Mayak Production Association is to provide information for activities aimed at environmental preservation in that territory. The priority tasks of the radioecological monitoring system are measuring all parameters of radiation impact on the environment (which contribute up to 95% of the total population exposure dose), and estimating all parameters required to support effective decision-making. The basic methods for radioecological monitoring are: unification and standardization of field and laboratory techniques for radionuclide analysis; measurement of gamma-irradiation dose rate; measurement of 137Cs, 90Sr, and plutonium concentrations in soils; measurement of radionuclide concentration in surface and ground waters and the atmosphere; study of the pathways of horizontal and vertical migration of radionuclides in natural media; and establishment of data bases including ecological mapping. Based on the information obtained, assessment of contamination and forecasts of the future radiation situation are prepared using models.

Air Pollutants, Radioactive↗

Environmental monitoring and ecological risk assessment for pesticide contamination and effects in Lake Pamvotis, northwestern Greece.

Monitoring of pesticide residues in water and sediments was conducted as a basis for subsequent ecotoxicological risk assessment for the shallow eutrophic Lake Pamvotis, northwestern Greece. During a one-year study period, atrazine, desethylatrazine (DEA), simazine, diazinon, malathion, oxamyl, carbofuran, and ethion were detected in water and atrazine, desethylatrazine, diazinon, and s-ethyl dipropylthiocarbamate (EPTC) in sediments, all at ppb concentration level. Temporal variation in pesticide concentrations was observed. Highest residue levels for most pesticides in both water and sediment matrices occurred in the May to July period with the exception of atrazine and DEA, which show highest levels in water during the September to November period. The ecological risk associated with pesticide contamination was assessed using two different methods: The toxic unit method, which provides a first indication of the relative contribution of detected pesticides to the total toxicity and a probabilistic approach, and the inverse method of Van Straalen and Denneman, which is used to quantify the ecological risk. The maximum percentage of the ecological risk was 10.3 and 51.8% for water and 17.2 and 70.6% for sediment, based on acute and chronic level, respectively. These results show that pesticides exert a significant pressure on the aquatic system of Lake Pamvotis, especially for the chronic-effect level. Simple quotient methods should be coupled with higher-tier risk assessment, especially if restoration activities on lake ecosystems are to be undertaken for sustainable development.

Animals↗