A qualitative sampling method for monitoring water quality in temporary channels or point sources and its application to pesticide contamination

A water-sampling device to monitor the quality of water periodically and temporarily flowing out of concrete tubes, sewers or channels is described. It inexpensively and easily enables a qualitative characterization of contamination via these point-source entry routes. The water sampler can be reverse engineered with different sizes and materials, once installed needs no maintenance, passively samples the first surge, and the emptying procedure is short. In an agricultural catchment area in Germany we monitored an emergency overflow of a sewage sewer, an outlet of a rainwater sewer and two small drainage channels as input sources to a small stream. Seven inflow events were analysed for 20 pesticide agents (insecticides, fungicides and herbicides). All three entry routes were remarkably contaminated. We found parathion-ethyl concentrations of 0.3 microg l(-1), diuron up to 17.3 microg l(-1), ethofumesate up to 51.1 microg l(-1), metamitron up to 92 microg l(-1) and prosulfocarb up to 130 microg l(-1).     

Competing TCE and cis-DCE degradation kinetics by zero-valent iron-experimental results and numerical simulation

The successful dechlorination of mixtures of chlorinated hydrocarbons with zero-valent metals requires information concerning the kinetics of simultaneous degradation of different contaminants. This includes intraspecies competitive effects (loading of the reactive iron surface by a single contaminant) as well as interspecies competition of several contaminants for the reactive sites available. In columns packed with zero-valent iron, the degradation behaviour of trichloroethylene (TCE), cis-dichloroethylene (DCE) and mixtures of both was measured in order to investigate interspecies competition. Although a decreasing rate of dechlorination is to be expected, when several degradable substances compete for the reactive sites on the iron surface, TCE degradation is nearly unaffected by the presence of cis-DCE. In contrast, cis-DCE degradation rates decrease significantly when TCE is added. A new modelling approach is developed in order to identify and quantify the observed competitive effects. The numerical model TBC (Transport, Biochemistry and Chemistry, Sch?fer et al., 1998a) is used to describe adsorption, desorption and dechlorination in a mechanistic way. Adsorption and degradation of a contaminant based on a limited number of reactive sites leads to a combined zero- and first-order degradation kinetics for high and low concentrations, respectively. The adsorption of several contaminants with different sorption parameters to a limited reactive surface causes interspecies competition. The reaction scheme and the parameters required are successfully transferred from Arnold and Roberts (2000b) to the model TBC. The degradation behaviour of the mixed contamination observed in the column experiments can be related to the adsorption properties of TCE and cis-DCE. By predicting the degradation of the single substances TCE and cis-DCE as well as mixtures of both, the calibrated model is used to investigate the effects of interspecies competition on the design of permeable reactive iron barriers. Even if TCE is present in only small concentrations (>3% of molar cis-DCE concentration) it is the contaminant limiting the residence time and the required thickness of the iron barrier.     

Enhanced experimental flexibility and control in ecotoxicological mesocosm experiments--a new outdoor and indoor pond and stream system

Scope The German Federal Environmental Agency has put into operation a new modular mesocosm system consisting of eight outdoor and eight indoor ponds and streams in order to investigate fate and effects of chemicals and municipal wastewater in aquatic ecosystems. General design and special characteristics are given to demonstrate the wide range of possibilities for experimental research. - General design. Each of the 16 streams with riffle and pool sections can be varied in length up to 106 m. The streams can be run as circular or flow-through systems at a flow velocity of 0.02 to 0.6 m/s. Physico-chemical standard parameters are measured on-line. The 16 ponds, which can be connected to the stream systems, are equipped with drainage and pore water-sampling devices for simulating processes in the littoral zone including influent and effluent ground water flow. Perspectives Since the highly flexible and controllable construction also allows treating a wide range of hydrological and ecological experiments external institutions are invited to submit proposals.     

Organic residue decomposition: The minicontainer-system a multifunctional tool in decomposition studies

The Minicontainer-test, first described by Eisenbeis (1993), was designed to study the kinetics of organic residue decomposition at a microsite level. It is derived from the litterbag technique and consists of polyethylene minicontainers (volume about 1.5 cm³) filled with a test substrate (litter, straw, cellulose, etc.). The minicontainers (MCs) are closed at either end with plastic gauze discs of variable mesh size (e.g. 20 μm, 250 μm, 500 μm or 2 mm). A definite number of such units are inserted into PVC-bars, which can be implanted into the soil horizontally or vertically, or be exposed on the soil surface horizontally. The bars are very stable and can be exposed in different environments for months to years. If required, the bars can be removed temporarily and stored, e.g. during soil cultivation. Should fresh litter be used, two phases of decomposition can be distinguished: a fast initial phase, which can be mainly related to the effect of leaching, and a second slow phase depending mainly on the activity of soil organisms and litter quality. Several questions can be addressed to investigations using MCs, e.g. 1) parts of the soil fauna which are involved in decomposition (nematodes, microarthropods, and smaller specimens of the macrofauna, e.g. enchytraeidae, diplopods and dipteran larvae) can be extracted from the litter substrate using a miniscale high gradient extractor, 2) the organic mass loss of litter can be determined, 3) microbial biomass (C_mic, N_mic) can be assessed by fumigation extraction and 4) microbial activity (respiration) in the test substrate can also be assessed by use of standardised methods. Compared to litterbag studies, the larger number of small replicate units improves the statistical evaluation. Until today the Minicontainer-test has been applied in forestry and agriculture, e.g. studying the effects of liming, soil restoration and the application of insecticides, e.g. Diflubenzuron (Dimilin) and Btk (Bacillus thuringiensis var.kurstaki).     

Daytime resolved analysis of polycyclic aromatic hydrocarbons in urban aerosol samples - impact of sources and meteorological conditions

Urban aerosol was collected in a summer and a winter campaign for 7 and 3 days, respectively. Low volume samples were taken with a time resolution of 160 min using a filter/sorption cartridge system extended by an ozone scrubber. Concentrations of mainly particle associated polycyclic aromatic hydrocarbons (PAH) and oxidised PAH (O-PAH) were determined by gas chromatography/high resolution mass spectrometry. The sampling site was located in the city centre of Augsburg, Germany, near major roads with high traffic volume. The daily concentrations and profiles were mainly governed by local emissions from traffic and domestic heating, as well as by the meteorological conditions. During the winter campaign, concentrations were more than 10 fold higher than during the summer campaign. Highest concentrations were found concurrent with low boundary layer heights and low wind speeds. Significant diurnal variation of the PAH profiles was observed. Enhanced influences of traffic related PAH on the PAH profiles were evident during daytime in summer, whereas emissions from hot water generation and domestic heating were obvious during the night time of both seasons. A general idea about the global meteorological situation was acquired using back trajectory calculations (NOAA ARL HYSPLIT4). Due to high local emissions in combination with low air exchange during the two sampling campaigns, effects of mesoscale transport were not clearly observable.     

Temporal variability in particle-associated pesticide exposure in a temporarily open estuary, Western Cape, South Africa

This study assesses the risk of current-use pesticides in a temporarily open estuary in South Africa by developing probabilistic risk estimates. Particle-associated pesticides (chlorpyrifos, prothiofos, cypermethrin, fenvalerate, endosulfan and p,p-DDE) and physicochemical parameters (salinity, temperature, flow, and total organic content (TOC)) were measured in the Lourens River estuary (Western Cape) twice a month over a period of two years and equilibrium partitioning theory was applied to calculate concentrations of pesticides in the water. The 90th percentile concentrations of pesticides associated to suspended particles and the calculated concentrations in water were 34.0microg kg(-1) and 0.15microg l(-1) for prothiofos, 19.6microg kg(-1) and 0.45microg l(-1) for chlorpyrifos and 18.6microg kg(-1) and 0.16microg l(-1) for endosulfan. Highest average concentrations were found around the summer season due to higher application rates and as a result of the low flow during this season. Species sensitivity distribution indicated a 1.5-2.8 times higher toxicity (hazardous concentration HC5) for marine organisms compared to freshwater organisms. The calculated concentrations in the water exceeded all threshold values suggested by international water guidelines. Chlorpyrifos and endosulfan posed the highest acute risk to the Lourens River estuary. No sufficient toxicity data and threshold values were found for prothiofos.     

Determination of 10 particle-associated multiclass polar and semi-polar pesticides from small streams using accelerated solvent extraction

A new analytical method using accelerated solvent extraction was developed for the determination of 10 particle-associated polar and semipolar pesticides. In addition, six deuterated analogues of the target compounds were evaluated as internal standards. The method yielded acceptable accuracy (73–103% recovery) and precision (<25% relative standard deviation) for eight compounds. Using size exclusion chromatography (SEC) as cleanup step resulted in higher recoveries compared to solid phase extraction (SPE) cleanup.

Deuterated standards with 10 or more deuterium atoms performed well as internal standards concerning similar recovery and correlation with the target analytes.

The method was employed to extract particle-associated pesticides from 16 streams located in an area with intense agriculture in France. Acetochlor, pirimicarb, tebuconazole, fenpropidin, -endosulfan and chlorfenvinphos were detected at concentrations up to 1 mg kg⁻¹ dry weight. A comparison with aquatic toxicity data indicated potential risk to the benthic fauna exposed to these concentrations of pirimicarb, -endosulfan and chlorfenvinphos.

We suggest that the method presented here be used for the extraction and quantitation of particle-associated polar pesticides.     

Remote sampling of a CO2 point source in an urban setting

High frequency CO₂ and wind speed measurements were used to examine the urban baseline eddy covariance CO₂ flux and analyse the CO₂ rich plume from a local power station. A reliable relationship between high frequency CO₂ maxima and the rate of CO₂ emission at the power station was established. This relationship was shown to be highly dependant on wind speed. The ensemble mean plume was found to be Gaussian in horizontal profile with a width dependant on wind speed. The relationship between peak CO₂ mixing ratio and averaging time was shown to be a simple power law with a time exponent of approximately 0.5. The large, short pulses in CO₂ mixing ratio in the power plant plume were found to have an approximately Lorentzian shape. These pulses generated negative vertical eddy flux measurements so data from the plume sector were necessarily excluded from the flux baseline results. The plume-excluded flux had a similar magnitude and variability to those reported in other urban CO₂ flux studies despite this site not being ideal due to the proximity of roughness elements to the measurement point.