Reversibility of stemflow-induced soil acidification in Swedish beech forest

Stemwater running down the trunks of beech (Fagus sylvatica L.) has an acidifying effect on soil near the stem. The deposition of acidifying substances may be two to four times higher close to the stem compared to in the stand in general. To study reversibility of soil acidification, 72 stumps of beech trees were chosen from five different year classes of felling (3, 6, 9, 14-15, 25-30), representing the years when stemflow ceased to affect the soil. The H(+) concentration (pH KCl) in the topsoil (0-5 cm) differed between the distances 10-30 cm and 230-250 cm from the stumps, the soil close to the stem being more acid. The longer the time since felling the smaller the differences in H(+) concentration became. This reduction in soil acidity amounted to ca. 50% after 15 years, and only small further changes occurred over the next ten years. This indicates that soil may not recover fully from acidification, or does so at a rather slow rate after the initial 15 years of recovery.     

Antagonism and synergism between lead and zinc in amphibian larvae

Lead and zinc effects on Bufo arenarum larval survival were studied in single and combined treatments. On a weight basis, lead is about twice as toxic as zinc. The antagonism or synergism between these heavy metals is dose-dependent.     

Reduction and avoidance of lubricant mist demands an integrated assessment approach

A case study to identify major factors for lubricant mist exposure covered 15 metal machining sites. The investigation included milling, turning, drilling and grinding applications. Systematic analysis considered all relevant data concerning the machine tool, the lubricant and the suction plant. The efficiency of the implemented maintenance program at the installed filter systems was checked by concentration measurements immediately before and after service. All performed measurements of lubricant aerosol and vapor loads upstream and downstream of the installed filter systems were carried out according to VDI 2066 and BIA 3110, respectively. The selection criteria for the sites to be investigated, the systematic nature of the data acquisition and the procedure of the analysis are demonstrated in detail by performing comparisons between selected applications using emulsions and those employing straight oil for lubrication. The results of the study identify recirculation of ventilated air as the major source of workplace exposure to airborne lubricant emissions. More than 60% of the demisters investigated emit air at total lubricant loads (aerosols and vapor) above the limit of 20 mg m-3 at any time of operation; which also means immediately after service. A common reason for exceeded aerosol loads in recirculated air is e.g. the fact that the type of filter system applied is often not suitable for the separation problem. Loads of lubricant vapor are usually higher at the processes which use water emulsions as lubricant. In a quarter of the cases the limits were exceeded solely due to high vapor loads even immediately after service. The exposure can be reduced by replacing the lubricant, installation of a vapor separation plant or avoiding air recirculation. Maintenance time of the demisting system and aerosol separation efficiency of state-of-the-art demisting systems can be expanded by implementation of enhanced preliminary filter stages. This study confirms that appropriate service measures lower both aerosol emissions and lubricant vapor concentrations due to the reduction of exposed oil-wetted surfaces. The performed measurements show no significant relationship between loads of airborne lubricants and the type of machining process. Therefore, investigations at a much more detailed level have to be performed. However, the individual assessment of any workplace due to the complex situation remains essential.     

Quantification of protein adducts of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride in human plasma

Hexahydrophthalic anhydride (HHPA) and methylhexahydrophthalic anhydride (MHHPA) are two highly allergenic compounds used in the chemical industry. A method was developed for quantification of protein adducts of HHPA and MHHPA in human plasma. The plasma was dialysed and the anhydrides were hydrolysed from the proteins at mild acidic conditions. The released hexahydrophthalic acid (HHP acid) and methylhexahydrophthalic acid (MHHP acid) were purified by reversed solid phase extraction followed by derivatisation with pentafluorobenzyl bromide. The derivatives were analysed using GC-MS in negative ion chemical ionisation mode with ammonia as moderating gas. As internal standards, deuterium labelled HHP and MHHP acids were used. The detection limits were 0.06 pmol mL(-1) plasma for HHP acid and 0.03 pmol mL(-1) plasma for MHHP acid. The between-day precisions for HHP acid were 18% at 0.3 pmol mL(-1) and 8% at 4 pmol mL(-1). For MHHP acid, the precisions were 13% at 0.3 pmol mL(-1) and 9% at 4 pmol mL(-1). There were strong correlations (r=0.94 for HHPA and 0.99 for MHHPA) between total plasma protein adduct concentrations and serum albumin adduct levels. Workers exposed to time-weighted average air levels of HHPA between < 1 and 340 microg m(-3) and between 2 and 160 microg m(-3) for MHHPA had plasma adduct levels between the detection limits of the methods and 8.40 and 19.0 pmol mL(-1), respectively.     

High frequency monitoring of the coastal marine environment using the MAREL buoy

The MAREL Iroise data buoy provides physico-chemical measurements acquired in surface marine water in continuous and autonomous mode. The water is pumped 1.5 m from below the surface through a sampling pipe and flows through the measuring cell located in the floating structure. Technological innovations implemented inside the measuring cell atop the buoy allow a continuous cleaning of the sensor, while injection of chloride ions into the circuit prevents biological fouling. Specific sensors for temperature, salinity, oxygen and fluorescence investigated in this paper have been evaluated to guarantee measurement precision over a 3 month period. A bi-directional link under Internet TCP-IP protocols is used for data, alarms and remote-control transmissions with the land-based data centre. Herein, we present a 29 month record for 4 parameters measured using a MAREL buoy moored in a coastal environment (Iroise Sea, Brest, France). The accuracy of the data provided by the buoy is assessed by comparison with measurements of sea water weekly sampled at the same site as part of SOMLIT (Service d'Observation du Milieu LIToral), the French network for monitoring of the coastal environment. Some particular events (impact of intensive fresh water discharges, dynamics of a fast phytoplankton bloom) are also presented, demonstrating the worth of monitoring a highly variable environment with a high frequency continuous reliable system.     

Development and validation of methods for environmental monitoring of cyclophosphamide in workplaces

Methods to monitor contamination of workplaces with antineoplastic drugs have been developed and validated. Cyclophosphamide (CP) was used as a model compound as it is one of the most commonly used antineoplastic drugs. A wipe sampling method to detect contamination with CP at surfaces was developed. A personal air sampling method to sample gas and vapour on solid sorbent tubes and particles with filters was also developed. Wipe and filter samples were extracted and sorbent samples were eluted, all with ethyl acetate. The samples were analysed with liquid chromatography tandem mass spectrometry. (2)H(6)-labelled cyclophosphamide was used as an internal standard. The between-day precision was 2-5% for wipe samples, 4-6% for sorbent samples and 3-8% for filter samples. The limit of detection was 0.02 ng CP per sample for the wipe and filter methods and 0.03 ng CP per sample for the solid sorbent method. Wipe sampling on surfaces made of different materials resulted in mean recoveries between 78-106%. The desorption recovery was between 97-102% for the wipe samples, 97% for the sorbent samples and 101% for the filter samples. Samples were stable for up to 2 months at 5 degrees C and -20 degrees C and for about 2 d at room temperature. The developed methods were applied to the measurement of contamination with CP in a hospital pharmacy. Trace amounts of CP, 1.3 and 1.4 ng, were detected on surfaces in the pharmacy.     

A combination of micro-porous membrane liquid-gas extraction and solid-phase trapping for ultra trace determination of benzene in urine

A method was developed for the determination of benzene in urine. The sample was pumped through the donor channel of a membrane extraction unit with a micro-porous membrane, separating the donor channel from an identical acceptor channel purged with nitrogen. The analyte reached the acceptor channel by diffusion through the membrane and was then swept by the carrier to a solid sorbent tube, where it was trapped. The analyte was subsequently thermally desorbed and analyzed by gas chromatography (GC) with mass selective detection (MS). After optimization, the recovery was close to quantitative, or 95%. Purging the membrane unit with pure water in between the samples eliminated any memory effects. The linearity was good in the concentration range examined (20-4000 ng l(-1)), with a correlation coefficient of 0.9996. The repeatability at 50 ng l(-1) and 400 ng l(-1) was 1.4% and 1.2%, respectively. The limit of detection was 12 ng l(-1) and the limit of quantification 35 ng l(-1). This enables assessment of benzene exposures of occupationally exposed subjects, of smokers and the majority of the general population. The developed method can be easily automated.     

Evaluation of forest nutrition based on large-scale foliar surveys: are nutrition profiles the way of the future?

This paper introduces the use of nutrition profiles as a first step in the development of a concept that is suitable for evaluating forest nutrition on the basis of large-scale foliar surveys. Nutrition profiles of a tree or stand were defined as the nutrient status, which accounts for all element concentrations, contents and interactions between two or more elements. Therefore a nutrition profile overcomes the shortcomings associated with the commonly used concepts for evaluating forest nutrition. Nutrition profiles can be calculated by means of a neural network, i.e. a self-organizing map, and an agglomerative clustering algorithm with pruning. As an example, nutrition profiles were calculated to describe the temporal variation in the mineral composition of Scots pine and Norway spruce needles in Finland between 1987 and 2000. The temporal trends in the frequency distribution of the nutrition profiles of Scots pine indicated that, between 1987 and 2000, the N, S, P, K, Ca, Mg and Al decreased, whereas the needle mass (NM) increased or remained unchanged. As there were no temporal trends in the frequency distribution of the nutrition profiles of Norway spruce, the mineral composition of the needles of Norway spruce needles subsequently did not change. Interpretation of the (lack of) temporal trends was outside the scope of this example. However, nutrition profiles prove to be a new and better concept for the evaluation of the mineral composition of large-scale surveys only when a biological interpretation of the nutrition profiles can be provided.     

Trihalomethanes in Drinking Water of Greater Québec Region (Canada): Occurrence, Variations and Modelling

The levels of trihalomethanes (THMs) – the main species of by-product from water chlorination – were monitored in thedistribution systems of the five major drinking water utilitiesof the greater area of Québec City in order to investigate andmodel their occurrence on a spatial and seasonal basis. Data forTHMs and other water quality and operational parametersassociated with their formation were generated through a 16 monthsampling program involving several sites representing variablewater residence times, from the plant to the system extremity.The results demonstrate that the differences in measured THMlevels between the five utilities are mainly due to the variablequality of raw waters, the type of water treatment process beingused and the type and levels of applied disinfectant. Dependingon the utility, average THM levels were from 1.3 to 2.5 timeshigher in the system extremities than in the water leaving thetreatment plant. Also, average levels of THMs measured in summerat the distribution system extremities were, depending on theutility, from 2.5 to 5 times higher than the average levelsmeasured in winter. The seasonal differences were found to besignificantly greater than those observed by others in waterutilities in the United States and Europe and are explained inlarge part by the considerable changes, over the year, in thequality and temperature of surface waters in Southern Québec. Forthe five utilities under study, multivariate regression modelswere developed in order to predict spatial and seasonalvariations of THMs. Both residual chlorine demand and temperaturewere found to be better, statistically, as predictors for THMoccurrence. The usefulness of the developed models for routineand long term water quality management, as well as for assessmentof human exposure to THMs, are also discussed.     

Competitive Retention of Lead and Cadmium on an Agricultural Soil

Lead and cadmium contamination of an agricultural soil has been studied using batch and column experiments. Thermodynamics of theretention phenomena may be represented by a Langmuir isotherm foran aqueous metal concentration up to 100 mg L^-1. First order kinetics with respect to the solid phase yield good predictabilityfor both batch and column experiments. Kinetics and thermodynamics of lead retention predominate over those ofcadmium. As a consequence, lead is preferentially retainedand can even displace sorbed cadmium. In the event of anspill involving both metals, cadmium would move further inthe soil and its aqueous concentration downstream could beeven higher than that of the influent solution, increasingpotential risks. A two-region model has been used to fit all the experimental results. Satisfactory predictions for column experiments are obtained with parameters which are consistent with those obtained for the batch experiments, for which sorption is described by a Langmuir isotherm including competitive retention.