Statistical models for evaluating suspected artefacts in long-term environmental monitoring data

Long-term water quality monitoring is of high value for environmental management as well as for research. Artificial level shifts in time series due to method improvements, flaws in laboratory practices or changes in laboratory are a common limitation for analysis, which, however, are often ignored. Statistical estimation of such artefacts is complicated by the simultaneous existence of trends, seasonal variation and effects of other influencing factors, such as weather conditions. Here, we investigate the performance of generalised additive mixed models (GAMM) to simultaneously identify one or more artefacts associated with artificial level shifts, longitudinal effects related to temporal trends and seasonal variation, as well as to model the serial correlation structure of the data. In the same model, it is possible to estimate separate residual variances for different periods so as to identify if artefacts not only influence the mean level but also the dispersion of a series. Even with an appropriate statistical methodology, it is difficult to quantify artificial level shifts and make appropriate adjustments to the time series. The underlying temporal structure of the series is especially important. As long as there is no prominent underlying trend in the series, the shift estimates are rather stable and show less variation. If an artificial shift occurs during a slower downward or upward tendency, it is difficult to separate these two effects and shift estimates can be both biased and have large variation. In the case of a change in method or laboratory, we show that conducting the analyses with both methods in parallel strongly improves estimates of artefact effects on the time series, even if certain problems remain. Due to the difficulties of estimating artificial level shifts, posterior adjustment is problematic and can lead to time series that no longer can be used for trend analysis or other analysis based on the longitudinal structure of the series. Before carrying out a change in analytic method or laboratory, it should be considered if this is absolutely necessary. If changes cannot be avoided, the analysis of the two methods considered, or the two laboratories contracted, should be run in parallel for a considerable period of time so as to enable a good assessment of changes introduced to the data series.     

First report on the uptake of automobile catalyst emitted palladium by European eels (Anguilla anguilla) following experimental exposure to road dust.

Following the introduction of automobile catalysts in the middle of the 1980s in Germany there is an increasing emission of the platinum-group-metals platinum, palladium (Pd) and rhodium. Still, it remains unclear if these metals are bioavailable for aquatic animals and to which extent they become accumulated by the aquatic biosphere. Because of analytical problems in detecting Pd in small biological samples the present investigation concentrates on the bioavailability of this metal. To answer the question of a Pd uptake by aquatic organisms experimental studies were conducted with European eels maintained in water containing road dust at a concentration of 10 kg/100 l. Following an exposure period of four weeks, samples of liver and kidney were analysed by total-reflection X-ray fluorescence analysis after co-precipitation of Pd with mercury. These experiments revealed an uptake of traffic related Pd by European eels which showed a mean liver Pd concentration of 0.18 +/- 0.05 ng/g (wet wt.), whereas the Pd concentration in the kidney ranged below the detection limit. Thus, in this study we can demonstrate for the first time that automobile catalyst emitted Pd is bioavailable for aquatic animals.     

Degradation of macrolide antibiotics by ozone: a mechanistic case study with clarithromycin

Macrolide antibiotics are widely used (in the order of 1g per person per year). They pass the body largely unchanged and are also not degraded in wastewater treatment plants. With not too much effort, they may be eliminated from their effluents by ozonation. The macrolide antibiotics have all a dimethylamino group at one of the carbohydrate residues in common. This functional group is the target of the ozone reaction, and clarithromycin has been selected here for a more detailed study. Since only the free amine reacts with ozone, the rate of reaction is pH dependent (at pH 7: k = 4 x 10(4) M(-1) s(-1)). In analogy to the ozonolysis of trimethylamine, the main reaction is a transfer of an O-atom yielding the N-oxide (identified by HPLC/MS-MS). A minor product (10%, based on formaldehyde yields) is demethylated clarithromycin (identified by HPLC/MS-MS). The dimethylamino group is thought to be essential for the binding of the macrolide antibiotics to their target. As a consequence, chemical changes of this functional group, notably the formation of the N-oxide that is no longer a proton acceptor, inactivates these drugs as assayed by the suppression of the growth of Pseudomonas putida. This is most important for wastewater treatment, as mineralization of clarithromycin by ozone would require 100 times as much ozone.     

Mapping heavy metals in polluted soil by disjunctive kriging

The soil of some 50 km(2) around the town of Weinfelden in north-east Switzerland has been sampled and analysed to estimate and map the concentrations of heavy metals before an incinerator for the canton's waste is built. Given that the estimates are subject to error, the probabilities that true values exceed the maximum tolerable concentrations of the Swiss federal guide have also been estimated by disjunctive kriging. These may now be used by the local planners for making decisions. Of the metals examined, lead exceeded the guide value at several sampling points, and a moderate probability of excess of lead is fairly widespread. Copper exceeded the guide value in vineyards and orchards, but also in a few places elsewhere, and the estimated probabilities of excess were not negligible. The other two metals of concern, cadmium (with one exception) and zinc, had concentrations much less than the guide values. The patterns of distribution of the four metals were similar, the product-moment correlations among them are substantial, except in the vineyards and orchards, and it seems likely that they had common sources.     

Reproductive biology and embryonic development of Eledone cirrosa (Cephalopoda: Octopoda)

Analyses of bottom trawl samples and feeding experiments in the laboratory revealed a reproduction period ranging from late March to early August in Eledone cirrosa of the Catalonian Sea (Western Mediterranean). The embryonic development, studies for the first time on eggs laid in the laboratory, shows no basic difference from that of other Octopodidae. The newly hatched animals are planktonic; morphologically, this feature is expressed by a relatively small arm-length.Laboratoire associé au C.N.R.S.     

Physiological and perceptual strain of firefighters during graded exercise to exhaustion at 40 and 10 °C

Purpose. To study whether perceptual identification should be included as a measure to evaluate physiological stress. Methods. Physiological variables oxygen uptake (V_O2), ventilation, heart rate, blood lactate concentration, rectal temperature (T_rec) and mean skin temperature, and perceptual variables rate of perceived exertion, thermal sensation and time to exhaustion, were measured at submaximal and maximal intensities during graded exercise on a treadmill to exhaustion in 12 firefighters wearing protective clothing and extra mass at 40 and 10 °C. Physiological strain index (PhSI) and perceptual strain index (PeSI) were calculated. Results. Apart from T_rec, all physiological and perceptual variables were higher at submaximal intensities of 40 °C. Time to exhaustion was 16% shorter and the corresponding V_O2 was reduced by 7% in the heat. A high correlation (r?=?89) between PhSI and PeSI was found at both temperatures. PeSI scores were equal to PhSI at both ambient temperatures, except at the two highest intensities in the heat, where PeSI was higher. Conclusions. These findings support use of perceptual identification to evaluate physiological stress. However, at very high intensities under hot conditions the perceptual strain was estimated higher than the physiological strain. More precise indexes are needed to include perceptual measures in safety standard.     

Indications of limited altered gene expression in Pinus sylvestris trees from the Chernobyl region

To evaluate the consequences of irradiation on the vegetation of the Chernobyl region, gene expression was compared in morphologically normal and dwarf needles from the same Pinus sylvestris trees in a region where the absorbed dose was 3-5 Gy. To compare the levels of gene expression, arrays consisting of 373 Pinus taeda cDNAs were hybridized with labeled cDNA derived from normal and dwarf needles of P. sylvestris. Twelve genes were significantly (P<0.01) up- or down-regulated between normal and dwarf needles for all five trees taken together. Five of these, related to stress or development, were up- or down-regulated 1.25-1.7-fold in the dwarf needles. There were no significant differences in (137)Cs content in the normal and dwarf needles, or in elongation growth rate of seedlings raised under controlled conditions from seed derived from trees in the region that had received a radiation dose over the range 2-12 Gy.