A study on the behaviour of pesticides and their transformation products in the Scheldt estuary using liquid chromatography-electrospray tandem mass spectrometry

Off-line solid-phase extraction (SPE) combined with liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS-MS) was used to study the estuarine behaviour of the polar pesticides, atrazine, chloridazon, diuron and metolachlor, and their transformation products (TPs), hydroxyatrazine (HA), desisopropylatrazine (DIA), desethylatrazine (DEA), 3,4-dichlorophenylmethylurea (DPMU) and monuron. The compounds were identified by comparing their LC retention times and product-ion spectra with those of standard solutions. In all but one case the detection limits of the method were sufficient to determine the compounds of interest over the entire salinity range in the estuary. The concentrations of the dissolved pesticides ranged from 70 ng l-1 for chloridazon to 1350 ng l-1 for diuron. The levels of TPs were 3-8% of the levels of their parent pesticide. The mixing plots of polar pesticides and their TPs indicated that TPs, which are present in fresh river water, are conservatively transported to the sea and that no additional amounts of TPs are formed during their transport through the estuary. The one exception was HA, of which approximately 10% of the amount transported to the North Sea is formed in the lower part of the estuary by photochemical oxidation of atrazine. The latter was concluded from the ratios of each analyte over the sum total of the parent pesticide and all TPs along the salinity gradient, which proved to be a useful tool for identifying such estuarine transformations.     

The influence of geometry and draught shields on the performance of passive samplers

Passive samplers provide an excellent opportunity to perform indicative measurements or establish a dense network of measuring sites. A drawback compared with conventional active measuring methods is the larger spread of results. This variation can, to a large extent, be attributed to the influence of temperature, sampler geometry and wind on sampling results. A proper design of sampler geometry and optimum choice of draught shield can reduce the influence of wind velocity on a badge type sampler to less than 10%. Wire mesh screens prove to be inadequate in damping turbulence. Filters give good results. Attention should be paid to the size and isolation value of the walls of the sampler to prevent thermal updrafts occurring within the sampler. Tube type samplers are less influenced by wind, provided that turbulence is prevented from influencing diffusion within the sampler.     

Global and Regional Distribution of Carbon Monoxide from MOPITT: Seasonal Distribution at 700 hPa

The Measurement of Pollution in the Troposphere (MOPITT) instrument is an eight-channel gas correlation radiometer, which was launched on the Earth Observing System (EOS) Terra satellite in 1999. Carbon monoxide (CO) is one of the important trace gases because its concentration in the troposphere directly influences the concentrations of tropospheric hydroxyl (OH), which controls the lifetimes of tropospheric trace gases. CO traces the transport of global and regional pollutants from industrial activities and large scale biomass burning. The global and regional distributions of CO were analyzed using the MOPITT data for East Asia, which were compared with the ozone distributions. In general, seasonal CO variations are characterized by a peak in the spring, which decrease in the summer. This work also revealed that the seasonal cycles for CO are at a maximum in the spring and a minimum in the summer, with average concentrations ranging from 118 to 170 ppbv. The monthly average for CO shows a similar profile to that for O3. This fact clearly indicates that the high concentration of CO in the spring is possibly due to one of two causes: the photochemical production of CO in the troposphere, or the transport of the CO into East Asia. The seasonal cycles for CO and O3 in East Asia are extensively influenced by the seasonal exchanges of different air mass types due to the Asian monsoon. The continental air masses contain high concentrations of O3 and CO, due to the higher continental background concentrations, and sometimes to the contribution from regional pollution. In summer this transport pattern is reversed, where the Pacific marine air masses that prevail over Korea bring low concentrations of CO and O3, which tend to give the apparent summer minimums.     

Exposure and inhalation risk assessment in an aluminium cast-house

To date the exposure, absorption and respiratory health effects of cast-house workers have not been described since most studies performed in the aluminium industry are focused on exposure and health effects of potroom personnel. In the present study, we assessed the external exposure and the absorbed dose of metals in personnel from the aluminium cast house. This was combined with an evaluation of respiratory complaints and the lung function of the personnel. 30 workers from an aluminium casting plant participated and 17 individuals of the packaging and distribution departments were selected as controls. The exposure was assessed by the quantification of total inhalable fume with metal fraction and by the determination of urinary aluminium, chromium, beryllium, manganese and lead concentration. Carbon monoxide (CO), carbon dioxide (CO2), aldehydes and polyaromatic hydrocarbons and man-made mineral fibres concentration were assessed as well. In order to evaluate their respiratory status each participant filled out a questionnaire and their lung function was tested by forced spirometry. Total inhalable fume exposure was maximum 4.37 mg m(-3). Exposure to the combustion gases, man-made mineral fibres and metal fume was well below the exposure limits. Beryllium could not be detected in the urine. The values of aluminium, manganese and lead in the urine were all under the respective reference value. One individual had a urinary chromium excretion above the ACGIH defined biological exposure index (BEI) of 30 microg g(-1) creatinine. There was no significant difference in any of the categories of the respiratory questionnaire and in the results of the spirometry between cast house personnel and referents (Chi-square, all p > 0.05). Exposure in cast houses seem to be acceptable under these conditions. However, peak exposure to fumes cannot be excluded and the potential risk of chromium and beryllium exposure due to the recycling of aluminium requires further attention.     

Prediction of Leachate Level in Kimpo Metropolitan Landfill Site by Total Water Balance

Kimpo metropolitan landfill has received various kinds of wastessince January 1992. The leachate level was measured to be 10.3 m in May 1995 and the level increased to 12.2 m in August 1996. Therefore, to prove the reason for the increasing leachate level, we calibrated hydraulic conductivity of each waste andintermediate layer using the HELP (Hydrologic Evaluation ofLandfill Performance) model. The leachate generation data measured from February 1993 to October 1995 was used in the model calibration. As a result of a model calibration, we obtained anaverage infiltration ratio and used this in analysis of the total water balance to predict elevation of leachate level. Main causes of the elevation of the leachate level were the high water content of the waste and the degradation of the leachate-drainage system caused by the subsidence of a naturalbarrier layer.     

Seasonal variations in nickel and vanadium in Mont Blanc snow and ice dated from the 1960s and 1990s

Ni and V have been determined in snow and ice collected at a high altitude location (Col du D?me) near the summit of Mont Blanc on the French-Italian border; dated from the 1960s and 1990s. Ni and V were simultaneously determined by inductively coupled plasma sector field mass spectrometry. Measured concentrations range from 6 to 700 pg g(-1) and 4 to 1,100 pg g(-1) for Ni and V, respectively. The results show pronounced seasonal variations in the concentrations of both metals, with high concentration values in summer layers and much lower values for winter layers. These seasonal variations are linked especially with the existence of inversion layers during winter months. Ni and V concentrations in excess of the contributions from rock and soil dust (Ni(excess), V(excess)) appear to be mainly associated with anthropogenic inputs, with pronounced seasonal variations. Large variations in the V(excess)/Ni(excess) ratio are observed, with a higher ratio in summer than in winter. This shows differences in anthropogenic inputs at Col du D?me during the different parts of the year. The above ratio was compared with the corresponding ratios for oil combustion from stationary sources and the exhaust from gasoline and diesel engines. It appears that Ni and V concentrations at Col du D?me are probably the result of changing combinations of contributions from oil combustion for power generation, industrial and residential uses, on one side, and automobile and truck traffic, on the other side, with possibly a significant contribution from Ni smelters in Russia during winter months.     

Microwave-Assisted Solvent Extraction of Air Particulates for the Determination of PAHs

A method for the determination of polycyclic aromatic hydrocarbons (PAHs) in air particulates using microwave-assisted solvent extraction (MASE) coupled to a microwave extraction system (MES) is proposed. During the period of August to October, 1994, Singapore was enveloped by haze caused by forest fires in Sumatra, Indonesia. Air sampling were carried out during September and October; the determination of ambient air PAH levels in Singapore was undertaken. PAH analysis by GC-MS provided excellent sensitivity, linearity of quantitation, peak identification. This technique was evaluated using certified reference materials (CRMs) HS-4 and HS-6. Good recoveries of PAHs (>73.3%) were obtained for both CRMs. The MASE technique using MES is suitable for the determination of PAH levels in ambient air with no clean-up step required.     

Field scale variability of cadmium and zinc in soil and barley

CaCl₂-extractable soil Cd and Zn contents have been suggested as a measure of bioavailability. To investigate the ability of this measure to reflect spatial patterns of Cd and Zn concentrations in barley (Hordeum vulgare L.) in an arable field, plant and soil samples were taken from a 0.5 ha area sandy soil contaminated with Cd and Zn. Cd and Zn contents in barley and yield were spatially variable. Yield was low, which may have been caused by Zn toxicity or atrazine turnover. For Cd, CaCl₂-extractable soil contents explained only 17% of the variation in Cd contents in grain, and for Zn no significant correlation was observed. Nevertheless, surface plots of CaCl₂-extractable soil contents and contents of barley grain illustrated their corresponding spatial patterns. Despite the poor linear correlation between CaCl₂-extractable soil-Cd and grain-Cd, a stochastic model for long term behaviour of Cd in field soils predicted observed variability in Cd contents of barley grain well from spatial variability of soil pH and organic matter content. The probabilistic model predicted behaviour of Cd in terms of probability, and was more appropriate than the deterministic approach.