Analytical protocol for the analysis of polybrominated dibenzo-dioxins and dibenzofurans: Data quality objectives and single-laboratory evaluation

An analytical protocol for the measurement of part per billion and sub-part per billion levels of PBDDs and PBDFs in selected flame retardant chemicals (polybrominated diphenyloxides; PBDPO) was developed. The fractionation/enrichment procedures were optimized to minimize the effects of the PBDPOs upon the ability to recover and measure the PBDD/PBDFs. Results from the method validation show that the current methodology is capable of accuracies ranging from 70% to 150% at the 0.1 to 10 ppb levels while larger sample sizes (from 20–200 mg to 4 g) are necessary in order to meet the EPA target Test Rule limit of quantification (LOQ) requirements.     

Effects of ultraviolet light (315 nm), temperature and relative humidity on the degradation of polylactic acid plastic films

The influence of temperature (30, 45 and 60 degrees C) and relative humidity (RH) (30%, 50% and 100%) on the degradation of poly(l-lactic acid) (PLA) films were studied. In addition, the effects of ultraviolet (UV) light (315 nm) on the degradation of PLA films were also analyzed. Various analytical techniques were applied to observe changes in the properties of PLA polymer films. FTIR spectroscopy was used as semi-quantitative method to get information about the chemistry of the degradative process. The degradation rate of PLA was enhanced by increasing temperature and RH, factors responsible for a faster reduction of the weight-average molecular weight (M(W)), of the glass transition temperature (Tg) and of the percentage of elongation at break. Moreover, UV treatment accelerated these phenomena.     

Quantitative determination of hexamethylene diisocyanate (HDI), 2,4-toluene diisocyanate (2,4-TDI) and 2,6-toluene diisocyanate (2,6-TDI) monomers at ppt levels in air by alkaline adduct coordination ionspray tandem mass spectrometry

Occupational exposures to isocyanates can lead to occupational asthma. Once sensitized, some workers could react to isocyanate monomers at concentrations below 1% of the Permissible Exposure Limit of 5 ppb in air. Currently available methods are not sufficiently sensitive to adequately evaluate isocyanates present at these levels in workplace air. This article describes a novel method for isocyanate determination allowing the ultratrace quantification in workplace air of hexamethylene diisocyanate, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate monomers. Sampling is performed during a complete workshift at a flow rate of 1 L min(-1) with a cassette containing a 1-(2-methoxyphenyl)piperazine-impregnated 25 mm filter. Analysis is performed using liquid chromatography hyphenated with coordination ionspray tandem mass spectrometry. The analytical method's linearity was measured for a concentration range varying from the limit of detection of 0.04-0.13 ng mL(-1), depending on the monomer, up to approximately 32 ng mL(-1) for every isocyanate monomer, all with correlation coefficients (R(2)) greater than 0.999. The analytical method's lower limit of quantification combined with an adapted sampling strategy allow the quantification of isocyanate monomers down to 0.04 ppt for an 8 h work shift when a lithium adduct is used, which is more than 300 times lower than the most sensitive method currently available. This novel method can be used to confirm the very low level of isocyanate monomers for the safe reassignment of sensitized workers and it is also useful for charting the isocyanate dispersion tail in workplace environments.     

Metal Contamination in Zebra Mussels (Dreissena Polymorpha) Along the st. Lawrence River

In order to evaluate the use of zebra mussels as biomonitors for metal bioavailability in the St. Lawrence River, we tested the hypothesis that the concentrations of 11 metals in zebra mussels vary significantly between sites along the river and that the season of collection and body size affect metal bioaccumulation. Mussels were collected at 14 sites during June 1996 and at monthly intervals at one site. Specimens were grouped in three size classes and their soft tissue was analyzed for As, Ca, Cd, Cr, Hg, Mn, Ni, Pb, Se, and Zn. Significant size effects were found for Ca, Cd, Cr, Cu, Ni and Zn. Spatial and seasonal variations in bioconcentration were significant for all metals. Spatial patterns in contamination that corresponded to known point sources of pollution or hydrology of the river were identified by principal component analysis. Seasonal variations can be attributed to the reproductive cycle of mussels and hydrological variability of the river. In comparison with values reported for zebra mussels in other contaminated sites in North America and Europe, levels of metal in the St. Lawrence River are low or intermediate. Our results show that when controlled for size and seasonal effects, zebra mussels represent a useful biomonitor for metal availability in the river and may offer an interesting alternative to native mussels and fish for such a role. Local contamination by some toxic metals is still a cause for concern in the St. Lawrence River.     

Amniotic fluid digestive enzymes: Diagnostic value in fetal gastrointestinal obstructions

The diagnostic value of amniotic fluid gamma-glutamyl-transpeptidase (GGTP) and intestinal alkaline phos-phatase (iALP) was evaluated in 55 patients who underwent amniocentesis for karyotyping because fetal gastric or small bowel dilatation had been detected by ultrasound. Gastrointestinal malformation was confirmed in 46 cases and there was no gastrointestinal anomaly in nine cases. Prenatal ultrasound was suggestive of gastroduodenal dilatation in 34 cases (group I) and small bowel dilatation in 21 cases (group II). In group I, amniotic fluid GGTP above the 99th percentile was 71 per cent sensitive and 100 per cent specific for a true anatomical defect of the digestive tract (mainly duodenal atresia). In group II, high levels of GGTP and/or iALP were 69 per cent sensitive and 83 per cent specific for a fetal digestive tract anomaly. In other words, when digestive tract dilatations were diagnosed by prenatal sonography, abnormal amniotic fluid enzyme activities were strongly suggestive of such an anomaly, the possibility of which was not precluded by normal amniotic fluid iALP and GGTP activities. But amniotic fluid digestive enzyme activities do not help in defining the prognosis.     

Forest productivity decline caused by successional paludification of boreal soils.

Long-term forest productivity decline in boreal forests has been extensively studied in the last decades, yet its causes are still unclear. Soil conditions associated with soil organic matter accumulation are thought to be responsible for site productivity decline. The objectives of this study were to determine if paludification of boreal soils resulted in reduced forest productivity, and to identify changes in the physical and chemical properties of soils associated with reduction in productivity. We used a chronosequence of 23 black spruce stands ranging in postfire age from 50 to 2350 years and calculated three different stand productivity indices, including site index. We assessed changes in forest productivity with time using two complementary approaches: (1) by comparing productivity among the chronosequence stands and (2) by comparing the productivity of successive cohorts of trees within the same stands to determine the influence of time independently of other site factors. Charcoal stratigraphy indicates that the forest stands differ in their fire history and originated either from high- or low-severity soil burns. Both chronosequence and cohort approaches demonstrate declines in black spruce productivity of 50-80% with increased paludification, particularly during the first centuries after fire. Paludification alters bryophyte abundance and succession, increases soil moisture, reduces soil temperature and nutrient availability, and alters the vertical distribution of roots. Low-severity soil burns significantly accelerate rates of paludification and productivity decline compared with high-severity fires and ultimately reduce nutrient content in black spruce needles. The two combined approaches indicate that paludification can be driven by forest succession only, independently of site factors such as position on slope. This successional paludification contrasts with edaphic paludification, where topography and drainage primarily control the extent and rate of paludification. At the landscape scale, the fire regime (frequency and severity) controls paludification and forest productivity through its effect on soil organic layers. Implications for global carbon budgets and sustainable forestry are discussed.     

Trophic relationships of white-chinned petrels from Crozet Islands: combined stomach oil and conventional dietary analyses

The diet of white-chinned petrels Procellaria aequinoctialis breeding at the Crozet Archipelago (southern Indian Ocean) was studied using two complementary methods: lipid analysis of stomach oils as trophic markers together with the conventional dietary approach (i.e., stomach content analysis). Objectives were (1) to investigate the adult diet when they feed for themselves by analyzing stomach oil lipids, and (2) to compare the lipid signature of chick and adult oils. Stomach oils mainly consisted of triacylglycerols (TAG), diacylglycerol-ethers (DAGE) and wax esters (WE) (66, 14 and 11%, respectively). The dietary origin of TAG and WE was evaluated by linear discriminant analyses with fatty acid and fatty alcohol fractions. Analyses evidenced that stomach oils did not originate from Antarctic krill, but instead from myctophid fish, thus demonstrating the importance of mesopelagic fish in the nutrition of adult petrels. This result was consistent with the identification of digested remains of myctophids recovered from adult stomach contents after long foraging trips. Large amounts of a rare lipid class, DAGE (up to 76% of total lipids), were identified in two stomach oils, together with fresh remains of the squid Gonatus antarcticus (99% by mass), suggesting that DAGE could have the potential to be trophic markers of cephalopods. Moreover, six oils probably originated from Patagonian toothfish, thus confirming strong interactions between white-chinned petrels and fisheries. Comparison between chick and adult stomach oils indicated no major differences in their biochemical composition suggesting an identical dietary origin of oils, mainly myctophids. Both adult and chick oils can therefore be used to determine the feeding ecology of adult birds when they feed far away from their breeding grounds. Finally, food analysis of chick samples and adult samples collected after short and long trips indicated different foraging grounds during the two kinds of trips, and also between long trips performed in subtropical and Antarctic waters.     

Chemical recognition of queen cells by honey bee workersApis mellifera (Hymenoptera: Apidae)

Summary Honey bee workers are able to nurse or to destroy and thus to recognize the capped queen cells containing a pupa. Fatty acid esters, especially methyl oleate, methyl palmitate and ethyl oleate were found in significant amounts on the queen pupal cuticle. Methyl oleate, the major component, along with smaller amounts of methyl linoleate and methyl linolenate, were involved in the recognition of queen cells by workers. In natural conditions of the colony, queen cells containing a paraffin pupal lure with methyl oleate were accepted 5.9 days by workers, releasing about 1.8 queen pupa equivalents during that period, when control cells (without ester) were kept only 2.1 days. Although these esters are non specific to honey bees, they are of great importance in social regulation of the honey bee colony.