Advanced Environmental Monitoring

Measurements of trace gas concentrations and other parameters like photolysis frequencies are a crucial tool for air pollution monitoring and the investigation of processes in the atmosphere. However, the determination of atmospheric trace gas concentrations constitutes a technological challenge, since extreme sensitivity (mixing ratios as low as 10

-13

) is desired simultaneously with high specifi city i.e. the molecule of interest usually must be detected in the presence of a large excess of other species. In addition, spatially resolved measurements are becoming increasingly important.

Today none of the existing measurement techniques meets all above requirements for trace gas measurements in the atmosphere. Therefore, a comprehensive arsenal of different techniques has been developed. Besides a large number of special techniques (like the ubiquitous short-path UV absorption for O

3

measurement) universal methods gain interest, due to their economy and relative ease of use. In particular, a single instrument can register a large number of different trace species.

The different types of requirements and the various techniques are discussed; special emphasis is given to spectroscopic methods, which play a large and growing role in atmospheric chemistry research. For instance, only spectroscopic methods allow remote sensing and spatially resolved determination of trace gas concentrations e.g. from space-borne platforms. Today many varieties of spectroscopic methods are in use (e.g. tunable diode laser- and Fourier-transform spectroscopy). The basic properties and recent applications of this technique are presented using differential optical absorption spectroscopy (DOAS) as an example. Future requirements and expected developments are discussed.

Keywords

: Air pollution monitoring, trace gas, DOAS, spectroscopy, remote sensing

This paper describes the recently developed United States Environmental Protection Agency (US EPA) test method that provides the user with unique methodologies for characterizing gaseous emissions from non-point pollutant sources. The radial plume mapping (RPM) methodology uses an open-path, path-integrated optical remote sensing (PI-ORS) system in multiple beam configurations to directly identify emission “hot spots” and measure emission fluxes. The RPM methodology has been well developed, evaluated, demonstrated, and peer reviewed. Scanning the PI-ORS system in a horizontal plane (horizontal RPM) can be used to locate hot spots of fugitive emission at ground level, while scanning in a vertical plane downwind of the area source (vertical RPM), coupled with wind measurement, can be used to measure emission fluxes. Also, scanning along a line-of-sight such as an industrial fenceline (one-dimensional RPM) can be used to profile pollutant concentrations downwind from a fugitive source. In this paper, the EPA test method is discussed, with particular reference to the RPM methodology, its applicability, limitations, and validation.

Keywords

: Area fugitive emission sources, open-path fourier transform infrared (FTIR), open-path tunable diode laser absorption spectroscopy (TDLAS), optical remote sensing (ORS), radial plume mapping (RPM)

Remote sensing techniques have been preferred for measurements of atmospheric trace gases because they allow direct measurement without pre- and/or post-treatment in the laboratory. UV–visible absorption measurement techniques have been used for ground-based remote sensing of atmospheric trace species. The multi-axis differential optical absorption spectroscopy (MAX-DOAS) technique, one of the remote sensing techniques for air quality measurement, uses scattered sunlight as a light source and measures it at various elevation angles by sequential scanning with a stepper motor. Ground-based MAX-DOAS measurements were carried out to investigate ClO, SO

2

and NO

2

levels in the mid-latitude coastal boundary layer from 27 May to 9 June, 2005, and SO

2

and NO

2

levels in fossil fuel power plant plumes from 10 to 14 January 2004. MAX-DOAS data were analyzed to identify and quantify ClO, SO

2

and NO

2

by utilizing their specifi c structured absorption features in the UV region. Differential slant column densities (dSCDs) for ClO, SO

2

and NO

2

were as high as 7.3 × 10

14

, 2.4 × 10

16

and 6.7 × 10

16

molecules/cm

2

(with mean dSCDs of 2.3 × 10

14

, 8.0 × 10

15

and 1.2 × 10

16

molecules/cm

2

), respectively, at a 3° elevation angle in the coastal boundary layer during the measurement period. Based on the assumption that the trace gases were well mixed in the 1 km height of the boundary layer, estimates of the mean mixing ratios of ClO, SO

2

and NO

2

during the measurement period were 8.4 (±4.3), 296 (±233) and 305 (±284) pptv, respectively. MAX-DOAS measurement of the power plant plumes involved making vertical scans through multiple elevation angles perpendicular to the plume dispersion direction to yield cross-sectional distributions of ClO, SO

2

and NO

2

in the plume in terms of SCDs. Mixing ratios based on the estimated cross-sections of the plumes were 15.5 (ClO), 354 (SO

2

) and 210 (NO

2

) ppbv in the plumes of the fossil fuel power plant.

Keywords

: Air pollution, chlorine monoxide, DOAS, remote sensing

There is an increasing need in many chemical sensing applications ranging from environmental science to industrial process control as well as medical diagnostics for fast, sensitive, and selective trace gas detection based on laser spectroscopy. The recent availability of continuous wave near infrared diode lasers-, mid-infrared quantum cascade and interband cascade distributed feedback (QC and IC DFB) lasers as mid-infrared spectroscopic sources addresses this need. A number of spectroscopic techniques have been demonstrated. For example, the authors have employed infrared DFB QC and IC lasers for the detection and quantification of trace gases and isotopic species in ambient air by means of direct absorption, cavity-enhanced, and photoacoustic spectroscopy. These spectroscopic techniques offer an alternative to non-spectroscopic techniques such as mass spectrometry (MS), gas chromatography (GC) and electrochemical sensors. The sensitivity and selectivity that can be achieved by both techniques (excluding electrochemical sensors) are similar, but the sensor response time, instrumentation size and cost of ownership for spectroscopic techniques can be advantageous as compared to MS-GC spectrometry.

Keywords

: Laser absorption spectroscopy, cavity-enhanced and photoacoustic spectroscopy, near infrared diode lasers, mid infrared quantum cascade lasers, chemical sensing of trace gases

Chemical ionisation reaction mass spectrometry (CIR-MS) is a more general version of proton transfer reaction mass spectrometry (PTR-MS) in which alternative chemical ionisation schemes are possible. This concept has been realised in a new instrument based on time-of-fl ight mass spectrometry (TOF-MS) and has been applied to the measurement of a range of trace atmospheric volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs) (Blake et al., 2004 and Wyche et al., 2005). Initial results have demonstrated the instrument to be capable of recording the entire mass spectrum in “real time” (ca. 1 min) with sensitivities in the order of 0.1 counts ppbV

-1

s

-1

in each unit mass channel. This article constitutes a brief overview of the CIR-TOF-MS instrument and several of its applications. A short account is also given of the “next generation” instrument which is under development. This new instrument will combine rapid beam modulation with Hadamard transformation of the detector output and should improve the detection sensitivity by more than an order of magnitude over the current CIR-TOF-MS instrument.

Keywords

: Proton transfer reaction mass spectrometry (PTR-MS), chemical ionisation reaction (CIR-MS) mass spectrometry, volatile organic compound, aerosol, Hadamard transform

We conducted continuous monitoring and the source identifi cation of carbon dioxide at Gosan, Seoul (Korea) and Yanbian during 2004–2005. The data reported are in situ continuous 1-year measurements of atmospheric CO

2

from the Gosan, Seoul and Yanbian stations. One-minute averages of near-surface atmospheric CO

2

concentration were obtained using a measurement system based on non-dispersive infrared (NDIR) analysis using the NOAA/ESRL (National Oceanic & Atmospheric Administration/Earth System Research Laboratory) standard with high precision monitoring data. The background CO

2

concentration of the complete measurement data was determined using the Advanced Global Atmospheric Gases Experiment (AGAGE) statistical pollution identifi cation procedure for removing pollution episode data. The background characteristics at Gosan are discussed in detail. The background concentration of CO

2

showed quite evident diurnal and seasonal variation. The diurnal variation shows a maximum in the nighttime and a minimum in the daytime, and the seasonal cycle shows a maximum in spring and a minimum in summer. Background data at Seoul and Yanbian also show a similar trend. In addition, we applied a hybrid receptor model driven by three-dimensional synoptic meteorology from the HYSPLIT4 (HYbrid Single-Particle Lagrangian Integrated Trajectory) model to determine CO

2

relative emission strength contributions from the Northeast Asia region as observed from Gosan. Modeling results from Seoul and Yanbian are also presented—they are important in creating a full potential source region map of the Northeast Asia region, as observations from Gosan are limited to the wind patterns crossing the station. Results indicate that there appears to be a large potential source region in the northeastern and eastern parts of China.

Keywords

: Carbon dioxide, continuous monitoring, emission strength, long-range transport, trajectory

Airborne gaseous and particulate matter was measured above downwind ocean areas from China to the western region of the Korean peninsula for 10 days in the spring and autumn of 2005.

The main objectives of this study were to investigate the spatial distribution of pollution in the ocean atmosphere between Korea and China, and to improve our understanding of acidic deposition in the Korean region in relation to processes affecting the transport of long-range trans-boundary air pollutants from China. The scientific payload on-board an ultra-light aircraft included measurements of the concentrations of SO

2

, NO

x

, O

3

and particulates. Meteorological profiles (air temperature, winds and humidity) were recorded simultaneously at a ground site.

A six-manned aircraft (PA-31-350 type) served the flight scenarios of eight altitude and two azimuth levels for measuring gas fluxes and particulate depositions in the first intensive observation period (IOP) during April 15–25 and a second period during October 15–25, 2005.

The overall mean concentrations of air pollutants in the atmospheric boundary layer were in the range 2.58–6.63 ppbv for SO

2

, 3.74–4.24 ppbv for NO

x

and 48.8–54.28 ppbv for O

3

in both observation periods. Measurements at different altitudes revealed that the pollutants were normally observed in high concentrations in the atmospheric boundary layer. However, the longitudinal measurements of SO

2

concentration showed higher values in areas over the Yellow Sea, though values decreased when approaching the Korean peninsula. Enhanced mass concentrations of SO

2

were observed for altitudinal measurements when a strong westerly air stream occurred in the low level boundary layer from China to Korea.

Aerosol number concentrations varied significantly in the range 32–4,640 ea/cm

3

for aircraft measurements during both periods. The differences in NO

x

level between aircraft and surface measurements play an important role in the chemical form and size of particulate matter.

Keywords

: Airborne gaseous, aircraft measurements, long-range trans- boundary, aerosol sulfate, air pollutants of SO2, NO

x

, O3

In this contribution, optical methods based on passive FTIR (Fourier Transform Infrared) and DOAS (Differential Optical Absorption Spectroscopy) techniques have been used to characterize the dispersion of gas emissions from industrial sources. Portable, zenith-looking, passive-DOAS instruments measured the horizontal distribution of an SO

2

plume from a power plant in a coastal town of Mexico. The column density of this gas was measured while making traversals across the plume with a car and a boat downwind from the emission source. The cross sections measured at different distances from the source are used to characterize the horizontal dispersion and to estimate emission fl uxes. In addition, a Scanning Infrared Gas Imaging System (SIGIS) was used to acquire passive IR spectra at 4 cm

-1

resolution in a two-dimensional array, from which a false-color image is produced representing the degree of correlation of a specifi c gaseous pollutant. The 24-h, real-time animations of the SO

2

plume help us to understand dispersion phenomena in various atmospheric conditions. The wealth of information retrieved from these optical remote sensors provides an alterative method for evaluating the results from plume dispersion models.

Keywords

: Industrial emissions, optical remote sensing, passive DOAS, passive FTIR, plume dispersion

The dust storm which is caused by low pressure activities in China and Mongolia has been investigated by many investigators, but very thin dust clouds, which can be frequently detected in every season (we call it background Asian dust here) by lidar in Japan, Korea, and China but not by satellite, have attracted very few investigators since detection of the cloud is not easy. It, however, has been suggested that the background Asian dust also plays an important role in the biogeochemical cycle of dust in east Asia and west Pacific regions through long range transport of dust particles by westerly winds, and information of outflow rate of background dust particles over the dust source areas is strongly desired since previous investigations were made mostly in the down wind regions (Iwasaka et al. 1988; Matsuki et al. 2002; Trochkine et al. 2002). According to the balloon-borne measurements made under the calm weather condition in 2001–2004 at Dunhuang (40°00′N, 94°30′E), China, mass flux of background Asian dust due to westerly wind was about 50 ton/km

2

/day over the Taklamakan desert (about 4 to 6 km altitudes) and total mass of mineral dust transported by westerly from the Taklamakan desert to downwind will be about 1.4 × 10

7

ton/year. From those values it is suggested that background Asian dust transported from the Taklamakan desert is very important and more investigations are desired to clarify the effect of the background Asian dust to environment and climate in east Asia and west Pacific regions.

Keywords

: Background Asian dust, background KOSA, balloon-borne measurement, mass flux of Asian dust particle

A variety of types of aerosol particles, both natural and human-made, are commonly suspended in the atmosphere. Different aerosol types have characteristic shapes, but basically fall into two categories: spherical and irregular. Haze and forest fi re smoke particles are examples of the former, and desert dust and biogenic debris (e.g., pollen) of the latter. It is shown here that the capability of polarization lidar systems to sense the exact shape of particles makes it a powerful tool to remotely identify many types of aerosols. This is particularly important in the study of how aerosols may affect the properties of clouds.

Keywords

: Aerosol backscattering, aerosol shape, polarization lidar

This paper describes a new method for retrieving path-averaged mass concentrations from multi-spectral light extinction measured by optical remote sensing (ORS) instruments. The light extinction measurements as a function of wavelength were used in conjunction with an iterative inverse-Mie algorithm to retrieve path-averaged particulate matter (PM) mass distribution. Conventional mass concentration measurements in a controlled release experiment were used to calibrate the ORS method. A backscattering micro pulse lidar (MPL) was used to obtain the horizontal extent of the plume along MPL’s line of sight. This method was used to measure concentrations and mass emission rates of PM with diameters ≤10 μm (PM

10

) and PM with diameters ≤2.5 μm (PM

2.5

) that were caused by dust from an artillery back blast event at a location in a desert region of the southwestern United States of America.

Keywords

: Fugitive dust, emission estimation, optical remote sensing, particulate matter, PM

10

, PM

2.5

, Mie theory, FTIR, transmissometer, micro pulse lidar

Geometrical, optical, and microphysical properties of free-tropospheric pollution have been determined with multiwavelength Raman lidar at Leipzig, Germany. Long-term observations carried out at fixed times (three times per week) since 1997 show advection of different aerosol types such as anthropogenic pollution from North America, forest-fire smoke from North America and Siberia, pollution from polar areas, and Saharan dust. Up to 45% off all regular observations indicate free-tropospheric pollution. On average, 20–25% of columnar optical depth was contributed by these layers. In extreme cases, the fraction of optical depth was considerably higher. At times pollution was found around 10–12 km height. Geometrical depth of the layers in many cases exceeded 1 km. Mean Ångström exponents of the layers varied from as low as 0.7 for Saharan dust to as high as 1.7 for anthropogenic pollution from North America. Individual measurements show significantly lower, respectively higher values. Lidar ratios in general were larger at 355 nm than at 532 nm. One remarkable exception is aged forest-fire smoke for which we find a reversed spectral dependence. Results for the Leipzig lidar site may be contrasted to results on European pollution outflow observed with Raman lidar at the southwest coast of Portugal. We also find strong differences with respect to South and Southeast Asian pollution observed during several field campaigns in the Indian Ocean.

Keywords

: Free troposphere, inversion, multiwavelength lidar, particle properties, pollution, Raman lidar, transport

As a result of the intrinsic nature of elastic light scattering aerosol particles, the non-monotonic size dependence of the scattered light intensity infl uences the function of most single optical particle counters and spectrometers. In order to tackle the problem of the varying response of single particle spectrometers when refractive indices of aerosol change, we developed a system utilizing two laser illumination sources with different wavelengths (533 nm and 685 nm) and four detectors collecting the forward and backward scattered light from both illuminating beams. The new method aims to determine the size and refractive index of particles typically occurring in the atmosphere. We successfully tested this new method numerically for its capability to simultaneously determine particle size in the range from 0.1 to 10 μm, the real part of the refractive index spanning from 1.1 to 2, and the imaginary part of refractive index between 0 and 1. The fi rst experimental results obtained with the prototype of the spectrometer verify the capability of the technique for accurate size measurement and real-time differentiation between non-absorbing and absorbing aerosol particles.

Keywords

: Atmospheric aerosols, optical measurement, particle size, refractive index

Active and passive remote sensing devices such as lidars and sunphotometers, respectively, are peculiar tools to follow the spatial and temporal evolution of aerosol loads and get complementary data to properly characterize aerosol optical and microphysical properties. A XeF-based Raman lidar is routinely used at the physics department of Lecce’s University (40° 20 ′N, 18° 6 ′E), to monitor aerosol vertical distributions and characterize aerosol optical properties by the vertical profiles of the backscatter and extinction coefficient, lidar ratio, and depolarization ratio. In addition, a sun/sky radiometer operating within AERONET is used to supplement lidar measurements and better infer aerosol types and properties by columnar values of the particle size distribution, the real and imaginary refractive index, the single scattering albedo and the Angstrom exponent (Å). The main objective of this paper is to provide some results on the spatial and temporal evolution of the aerosol properties over south-east Italy, in the central-east Mediterranean basin, by using lidar and sunphotometer measurements. Specifi cally, results on the characterization of the aerosol load from July 18 to July 21, 2005 are reported and particular attention is devoted to the Sahara dust outbreak that has occurred over south-east Italy on July 18 and 19, 2005.

Keywords

: Aerosols, lidar, remote sensing, sunphotometer

Environmental control of pollution uses concentrations of particulate matter (PM) for evaluation of the pollution load. Retrievals of PM from satellite observations are supplementary information to ground-based national observation networks. A method of PM determination using retrievals of spectral aerosol optical thickness is described. The method has been applied to MERIS L1 data over Germany. PM retrievals from satellite observations have been compared with ground-based PM10 measurements of the Federal Environmental Agency, Umweltbundesamt (UBA).

Keywords

: MERIS, PM10, BAER, AOT, aerosol

The biological aerosol threat has become a major military and civilian security challenge, primarily due to the increased accessibility to biological technologies, and perhaps partially due to technical difficulties in developing effective detection systems. Defence Research and Development Canada (DRDC) has investigated various technologies, including point and standoff systems for environmental aerosol monitoring, to enhance readiness for such threats. Standoff bio-aerosol systems were based on infrared techniques and laser-induced fluorescence (LIF) approaches. These LIDAR systems were designed to monitor the atmosphere from a standoff position, measuring light scatter or fluorescence signals originating from particle-based biological molecules. In the case of LIF, the signal is spectrally resolved by a combination of grating elements and a range-gated intensified charge couple device (ICCD) that records the spectral information within a range-selected atmospheric volume. Multivariate data analysis techniques may be used to achieve real time detection. Advanced data processing techniques combined with the sensitive sensor have demonstrated the potential to detect and discriminate a mixture of several biological species. Instrument detection limits were determined to be within the target range specified for military and civilian scenarios. The potential of this innovative sensor to measure spectral data of various biological agent simulants, interferants and ambient bio-aerosols of natural and anthropogenic origins will be discussed. The detection limits obtained with this new sensor during open air releases for several given materials, cloud depths and ranges were assessed.

Keywords

: Agent simulants, biological aerosol, LIF, range-gated CCD, standoff detection

Atmospheric aerosol optical thickness (AOT) was retrieved over urban areas using moderate resolution imaging spectroradiometer (MODIS) 500-m resolution calibrated radiance data. A modifi ed Bremen Aerosol Retrieval (BAER) algorithm was used to retrieve AOT over Seoul, Korea. Since the surface refl ectance of an urban area is typically brighter than that of vegetation or soil areas in the visible wavelength region, the error associated with aerosol retrieval is higher. Surface refl ectance determination using the linear mixing model (LMM) produced values that were smaller (~0.02) than those obtained using the minimum refl ectance technique (MRT). This difference would lead to an overestimated AOT when using the LMM approach. Retrieved AOT data using MRT and standard MODIS 10-km aerosol products (MOD04) were compared to Rotating Shadow-band Radiometer (RSR) observations at Yonsei University, Seoul, Korea. Regression analysis showed that the root mean square error (RMSE) of MODIS AOT and MOD04 AOT was 0.05 in both cases. In addition, MODIS AOT data were compared with ground-based particulate matter data (PM10) from air quality monitoring networks of the National Institute of Environmental Research (NIER). MODIS AOT data showed a relatively low correlation (

r

= 0.41) with surface PM10 mass concentration data due to differences in ground-based and column-averaged data, variability of terrain, and MODIS cloud mask. This result is similar to that of other investigations. The application of fi ne-resolution satellite data supports the feasibility of local and urban-scale air quality monitoring.

Keywords

: AOT, LMM, MODIS, MRT, PM10

Aquatic colloids are ubiquitous in all kinds of natural water and in general found to be small in size (<100 nm) and low in number density (<10

14

particles per liter). Colloids of such properties may play a significant role for the aquifer migration of environmentally hazardous contaminants: radioactive elements as well as other trace chemical composites. Insightful knowledge on aquatic colloids is therefore perceived as indispensable for monitoring the environmental behavior of hazardous trace constituents.

This chapter describes the chemical process of generating aquatic colloids, e.g. their kernels like hydroxy aluminosilicate (HAS) colloids, as well as the incorporation of radionuclides into such colloid formation. Likely processes are characterized in particular by a combination of different nanoscopic approaches. The colloid formation is monitored radiochemically in conjunction with the highly sensitive spectroscopic speciation, e.g. time-resolved laser fluorescence spectroscopy (TRLFS), which facilitates the chemical characterization of trace actinides in particular. Colloids thus generated are quantified for their average size and number density by laser-induced breakdown detection (LIBD) upon optical plasma monitoring. Exemplary illustrations are summarized for the formation of colloid-borne trivalent actinides (Am, Cm), which become incorporated into HAS-colloids. Discussion is extended to the migration behavior of radionuclides as colloid-borne species in natural aquifer systems, for which a field experiment is chosen as a case in point.

Keywords

: Aquatic colloids, speciation, actinides, migration, environmental monitoring

Earthworms are regarded as one of the most suitable animals for testing the toxicity of chemicals in soils and have been adopted as standard organisms for ecotoxicological testing. In several guidelines concerning earthworm toxicity tests,

Eisenia fetida/andrei

(

E. fetida/andrei

) was chosen because it can be easily cultured in the laboratory and an extensive database on the effects of all classes of chemicals exists for this species. Acute and chronic toxicity tests have been used traditionally to assess the toxicity of contaminants, with mortality and changes in biomass, reproduction rates and behavioral responses representing endpoints. Moreover, the avoidance behavior test (AVT) using earthworm is under development and standardization, which records the ability of earthworms to choose or avoid a certain soil. Recent studies have shown that neutral red retention time (NRRT) has the potential for a rapid assessment of the toxic effects for earthworms of soils contaminated with heavy metals and metalloids. Toxicity is the apparent expression of the metal accumulation in earthworm body. The uptake, accumulation and elimination properties of metals by earthworm are the major part of toxicology, which is called toxicokinetics. Geochemical factors may have signifi cant effects on metal transport or bioavailability. Prediction models for metal accumulation and toxicity in soils are being developed based on metal bioavailability. In this study, methodologies and research trends in earthworm toxicity are reviewed for understanding metal bioavailability. Toxicity prediction models are introduced for terrestrial environment and several studies are referred to understand the role of geochemistry in toxicology.

Keywords

: Bioavailability, earthworm toxicity, metal, prediction model, toxicokinetics

In this study, the characteristics of effluent organic matter (EfOM) were investigated and differentiated from natural organic matter (NOM) using several analytical methods: XAD resin fractionation, size-exclusion chromatography in combination with a dissolved organic carbon detector (SEC–DOC), fluorescence spectroscopy (excitation-emission matrix [EEM] and fluorescence index [FI]), biodegradable dissolved organic carbon (BDOC) testing, ultraviolet absorbance at 254 nm (UVA

254

), and DOC measurements. Also, the impact of EfOM on drinking water sources was evaluated in terms of treatability of the EfOM by a drinking water treatment process. Treatability experiments were carried out with various mixtures of NOM and EfOM by a coagulation process. Characterization results indicated that the distinct properties of EfOM were lower specific UVA (SUVA), more hydrophilic organic matter, increased FI values, higher polysaccharides peak in SEC, and clear protein-like peak in EEM, as compared to NOM. Removal of DOC in EfOM-dominated waters by coagulation was not as high (~38%) as those of NOM samples (~57%), which was attributed to the higher hydrophilicity of EfOM. BDOC of EfOM occurred primarily via degradation of microbially derived organic constituents, such as proteins and polysaccharides.

Keywords

: Natural organic matter, effluent organic matter, drinking water treatment

This study was conducted to illustrate an innovative method for the optimization and control of the ozone-AOP (advanced oxidation process) to achieve the target oxidation objective for the removal of hazardous micropollutants, while minimizing the formation of harmful by-products, bromate (BrO

3

). The control method was based on a specifically conceived analytical setup with FIA (flow injection analysis), which can accurately isolate and measure an individual oxidant in the presence of other oxidants (ozone, hydrogen peroxide, free chlorine, etc). Three auto-analyzing units (Ozone Kinetic Analyzing Unit, Hydrogen Peroxide Analyzing Unit and Bromate Analyzer) were specially devised for this study, which were successfully tested on both in lab- and demoscales for in-plant operation.

Keywords

: Bromate, ozone, ozone/hydrogen peroxide, hydroxyl radical (OH•), optimization

Results of online investigations of water quality during a water treatment process by ultraviolet-laser-induced fl uorescence (UV-LIF) are presented. In the fi rst part the integrated fl uorescence intensity is correlated to the classically determined concentration of dissolved organic carbon (DOC). Decision, detection and determination limits are evaluated for this procedure and online DOC measurements conducted with the presented LIF system are compared to reference analysis. In the second part the ozone demand in the water treatment process is derived from the LIF-signal directly. The calibration was done by correlating LIF-signals with the ozone doses for different conditions and a defi nite residual ozone concentration in the processed water.

Keywords

: Dissolved organic carbon (DOC), drinking water, laser induced fluorescence, online process control, real-time measurements

Sensors and biosensors as well as biochemical responses (biomarkers) in ecosystems owing to environmental stress provide us with signals (environmental signalling) of a potential damage in the environment. These responses are perceived in this early stage, but in ecosystems, the eventual damage can be prevented. Once ecosystem damage has occurred, the remedial action processes for recovery could be expensive and pose certain logistical problems. Prevention of ecosystem deterioration is always better than curing. Ideally, “early warning signals” in ecosystems using sensing systems and biochemical responses (biomarkers) would not only tell us the initial levels of damage, but these signals will provide us as well with answers to develop control strategies and precautionary measures with respect to the water framework directive. To understand the complexity of the structure of populations and processes behind the health of populations, communities and ecosystems, we have to direct our efforts to promote rapid and cost-effective new emerging parameters of ecological health. New emerging parameters are biochemical effect (biomarker) related parameters in the field of immunotoxicity and endocrine disruption. Environmental effects such as genotoxicity and clastogenicity were detected in organisms from various “hot spots”. Vital fluorescence tests are one means that allow us to unmask adverse events (i.e., genetic alterations in field-collected animals or in situ-exposed organisms) by a caging technique. New emerging ecosystem health parameters are closely linked to biomarkers of organisms measured in monitored areas. One problem is always to find the relevant interpretation and risk assessment tools for the environment.

Keywords

: Biosensor, effect assessment, ecotoxicological classification in sediment, endocrine effects, assessment of “good ecological status”, drug exposure.

A new methodology for simple, rapid, high throughput biological testing of potentially hazardous chemical and environmental samples has been developed, which is based on measurement of oxygen consumption of aquatic test organisms using phosphorescent oxygen-sensitive probes and detection on a fluorescent plate reader. Test organisms are exposed to potential toxicants and then allowed to respire in a sealed measurement compartment in the presence of soluble oxygen probe added to the sample. The resultant depletion of the dissolved oxygen causes an increase in sample fluorescence over time, thus reflecting the organism respiration rate and its alterations. Dedicated low-volume sealable 96-well plates provide improved sensitivity, convenience and miniaturization in such respirometric assays. These assays are carried out using standard laboratory tools and fluorescence plate readers, with multiple samples processed in parallel in 96-well microtitter plates. Oxygen consumption rate is a universal biomarker of general viability and metabolic responses of aerobic organisms, hence, this methodology is applicable to various organisms, including those currently used in toxicity testing. In this study, the new respirometric platform has been demonstrated with different organisms including prokaryotes (

E.coli

), eukaryotes (Jurkat T-cells), invertebrates (

Artemia salina

), and validated with toxicity testing of environmentally relevant chemicals. A panel of water samples discharged from wastewater treatment plants was also analyzed with this panel of test organisms. Organisms were exposed to the samples for a period of time (0–24 h depending on the organism chosen), and then assessed for their respiration rates (1 h assay). Toxicity was recorded as EC

50

, i.e., the concentration of the toxicant which caused a 50% decrease in the respiration compared to untreated organisms. Responses of various organisms to certain chemicals can be cross-compared and correlated to established toxicity tests (based on LD

50

). In terms of sample throughput, sensitivity, speed, flexibility and convenience, the new screening platform is seen as being superior to the existing toxicity tests currently used. It provides adequate assessment of biological hazards of complex chemical and environmental samples, allows for the monitoring of sub-lethal effects and provides information-rich data reflecting the mode of toxicity. It is therefore highly suitable for environmental monitoring and screening of potentially hazardous samples, including large scale programs such as EU Water Framework Directive and REACH.

Keywords

: Toxicity testing, animal-based testing, oxygen consumption assay, fluorescence-based oxygen sensing, optical oxygen respirometry

The yeast

Saccharomyces cerevisiae

is one of the most characterized eucaryotes and its complete genome sequence was published in 1986. Thus, this organism is a good candidate for biological environmental monitoring. Omics (genomics, proteomics, metabolomics) technology is being applied to biological studies from prokaryotes to humans. We are applying omics technologies to environmental monitoring using yeast cells, medaka, rice, rat, and mouse. In this report, we focus on yeast omics as tools of environmental monitoring for chemicals, radiation, and physical stresses in yeast. For genomics studies, we use commercially available DNA microarrays. We analyzed the expression profiles for highly induced or repressed genes, the functional characterization of induced and repressed genes, and cluster analysis. The list of highly induced and repressed genes can help to identify candidate biomarkers and strongly induced functions; however, this may reflect only a small part of the full stress response. The functional characterization studies, on the other hand, can help elucidate the mechanisms of stress response. Cluster analysis allows comparison of different environmental stress conditions. For proteomics studies, classical two-dimensional electrophoresis and peptide sequencing or mass spectrometry were used for monitoring stress induced and modified proteins. However, protein turnover ratio and especially degradation rates were slow in yeast cells and the induction levels of proteins do not always reflect the physiological status of the cell. The role of proteomics in yeast cells must be focused on modification of proteins. For metabolomics studies, capillary electrophoresis/mass spectrometry (CE/MS) was used for the separation and identification of metabolites. This new methods have high potential for the evaluation of environmental stress.

Keywords

:

Saccharomyces cerevisiae

, environmental stress, OMICS, genomics, proteomics, metablomics, DNA microarray, CE/MS

Endocrine disrupting chemicals (EDCs) are of concerning chemicals due to their ability to make damage or alter hormonal activities in living organisms. In this study, therefore, toxicogenomic analyses using a real time RT-PCR technique have been conducted to characterize the responses of male Japanese Medaka and to provide valuable information about the toxicological properties and their hazardous effects of three EDCs, i.e., 17-beta estradiol (E

2

), nonylphenol (NP) and bisphenol A (BPA), to Japanese medaka fish. For doing that, the expression kinetics of female-related genes and other cellular toxicity representative genes, including vitellogenin (yolk protein precursor), choriogenin L (inner membrane precursor of egg), cytochrome P450 1A (CYP1A) and heat shock protein 70 (HSP70) were used. Gene expression levels at three different times after exposure with two different concentrations of EDCs were quantified by measuring messenger RNA (mRNA) concentrations in the liver extracts using the Taqman based real-time PCR method. The results showed that E

2

causes a strong estrogenic effect even at a concentration of only 1 ppb, while NP and BPA were found to cause some form of cellular toxicity, and an estrogenic effect with inducing the production of HSP 70, respectively.

Keywords

: Choriogenin L, endocrine disrupting chemicals,

Oryzias latipes

, real time PCR, vitellogenin, 17-beta estradiol (E

2

), bisphenol A (BPA), cytochrome P450 1A (CYP1A), heat shock protein 70 (HSP 70), nonylphenol (NP)

Optical detection method based protein chips for detection of the various pathogens such as

Escherichia coli

O157:H7,

Salmonella typhimurium

,

Yersinia enterocolitica

, and

Legionella pneumophila

in contaminated environment were developed. In order to endow the orientation of antibody molecules on solid surface, protein G was introduced. Gold (Au) surface was modifi ed with 11-mercaptoundecanoic acid (11-MUA) and the protein G was immobilized on the Au surface. And the spots of different antibodies against pathogens (

E. coli

O157:H7,

S. typhimurium

,

Y. enterocolitica

, and

L. pneumophila

) on protein G of Au surface were arrayed using a microarrayer. The responses of the various pathogens such as

E. coli

O157:H7,

S. typhimurium

,

Y. enterocolitica

, and

L. pneumophila

to the protein chip was investigated by surface plasmon resonance (SPR), fl uorescence microscopy and imaging ellipsometry (IE). The lowest detection limit of the fl uorescence based protein chip was 10

2

CFU/mL and the protein chip using IE could successfully detect the pathogens in concentrations varying from 10

3

to 10

7

CFU/mL.

Keywords

: Fluorescence microscopy, imaging ellipsometry, protein chip, pathogen, protein G, surface plasmon resonance

Gene profiling of Japanese medaka (

Oryzias latipes

) was performed using an oligonucleotide DNA microarray representing 26,689 TIGR

Oryzias latipes

Gene Indices (OLGIs). We first confirmed the high correlation coefficients (>0.94) of gene expression in individual medaka grown under the standard procedures. Secondly, we exposed male medaka to estrogenic compounds [17β-estradiol (E2), 17α-ethynylestradiol (EE2), nonylphenol (NP), octylphenol (OP), and bisphenol A (BpA)], and assessed estrogenic compounds-induced changes in mRNA expression with the medaka microarray. Histological analysis showed the production of testisova in the testes of male medaka exposed to the estrogenic chemicals. Microarray analysis of the chemical-treated male medaka identified estrogenic compoundsresponsive OLGIs, although many of those OLGIs were not sex-specific. Based on the mRNA expression profiles, assessment of the degree of feminization/demasculinization using the combination of Pearson correlation coefficient (CC) and Euclidean distances was also attempted in order to estimate the impact of hormonally active chemicals. The calculated feminization factors indicate that E2 and EE2 treatment “weakly feminized” male medaka (~50%), while NP, OP, or BpA treatment did not significantly feminize male medaka (<6%). On the other hand, the calculated male-dysfunction factors suggest that male physiological functions were disrupted by the EE2 exposure (~50%), but not significantly by E2, NP, OP, or BpA treatments (<16%). Results demonstrate the possibility of using medaka microarrays to estimate the overall effects of hormonally active chemicals.

Keywords

: DNA microarray, endocrine disrupter, feminization, masculinization, medaka

Using the spontaneous locomotor behaviour of fi sh as a toxicological parameter, sublethal effects to the naturally occurring cyanotoxin microcystin-LR (MC-LR) and a characteristic man-made chemical 2.4.4′-trichlorobiphenyl (PCB 28) were investigated under laboratory conditions. Swimming activity of two fi sh species (

Danio rerio

and

Leucaspius delineatus

) was monitored continuously by using an automated video-monitoring and object-tracing system. For analysing cyclic aspects the basic behavioural analyses were combined with chronobiological procedures such as power spectral analysis. Using these methods it was shown that dissolved MC-LR concentrations between 0.5 and 50μ g l

-1

and PCB 28 concentrations at 100 and 150μ g l

-1

acted as stressors and caused signifi cant changes in the behaviour and circadian activity rhythms of

Danio rerio

as well as

Leucaspius delineatus

. For both species elevated concentrations of the stressors led to a reduction of their activity. It was proved that the basic behavioural analyses combined with chronobiological procedures could be valuable tools for the study of stressful or even harmful environmental factors in the fi eld of ecotoxicology as well as for biomonitoring. Some fi ndings of this study build the basis for the development of a new low-budget fi sh biomonitoring system for drinking water protection.

Keywords

: Behavioural ecotoxicology, fish, chemical stressors, early warning systems of drinking water quality

Contaminants’ presence in the aquatic environment is relevant for the disturbance of the European stocks of diadromic species. The main goal of this study was to compare the biotransformation and oxidant/antioxidant

status

of yellow eel (

Anguilla anguilla

) populations from the estuaries of Minho (reference), Lima and Douro (contaminated) Rivers. Comparatively to the values determined in eels from the reference estuary, low total glutathione and reduced glutathione levels associated with high lipid peroxidation levels and benzo(a)pyrene-type metabolites’ concentrations were found in liver from eels collected in the estuary of Lima river. Eels from Douro estuary showed high liver ethoxyresorufi n-

O

-deethylase, catalase, glutathione peroxidase, total glutathione, reduced glutathione and oxidized glutathione levels associated with low lipid peroxidation and benzo(a)pyrene-type metabolites relatively to fi sh from the reference estuary. The pollution present in the estuaries of Lima and Douro Rivers is causing alterations on biotransformation and antioxidant stress parameters. In addition, Lima estuary eels are exposed to polycyclic aromatic hydrocarbons as indicated by the high levels of metabolites found. Since polycyclic aromatic hydrocarbons interfere with reproductive parameters and increased cytochrome P450 1A1 activity (as found in eels from the Douro estuary) interfere with reproduction, the exposure of eels to pollution in Lima and Douro estuaries may be decreasing their reproductive potential. In addition, energy to face chemical stress may be allocated from processes such as growth and weight increase that are factors determinant for the success of the long migration to the reproduction area. Therefore, pollution may be decreasing the contribution of these populations to the species evolution.

Keywords

: Biomonitoring, biomarkers, biotransformation, oxidative stress,

Anguilla anguilla

The aim of this study is to analyse the toxicological potential of fine and ultrafine particles from industrial combustion processes using a biotest. This biotest is performed by near-realistic exposure of cultivated lung cells at the air-liquid interface and analysing the biological responses. Important steps in this work are to develop the exposure system for the use at industrial particle sources, to provide reproducible deposition conditions for submicron particles and to validate the exposure protocol for the bioassay. The presented technique maintains the viability of the cells but is sensitive for inflammatory effects. Exposure experiments with the ultrafine fraction of fly ash from a municipal waste incinerator have shown an increased release of IL-8 as a function of exposure time and dose. The presented exposure method and the lung specific bioassay seem to be an appropriate model to simulate the inhalation of particulate air pollution and to screen the biological effects of particulate emissions from different sources.

Keywords

: Aerosol, bioassay, PM10, toxicity, ultrafine particles