Pyrrolizidine alkaloids on three trophic levels – evidence for toxic and deterrent effects on phytophages and predators

Summary. Pyrrolizidine alkaloids (PAs) present a model system in the investigation of tritrophic interactions mediated by plant secondary compounds. However, their toxicity for insect herbivores has never been experimentally proven. Here, we demonstrate the toxic effects of a PA on growth and survival of the eri silk moth Philosamia ricini. In a feeding experiment, larvae of this generalist herbivore fed with an artificial PA diet gained weight significantly slower than control animals, and died as pupae. We suggest that derivatives of the ingested PA N-oxide damage developmental functions during metamorphosis. A tracer test with [¹⁴C]senecionine N-oxide revealed that the caterpillars lack adaptations that would prevent conversion of the chemical into the pro-toxic free base. In contrast, the PA adapted leaf beetle Longitarsus anchusae accumulates PAs as N-oxides. We tested the purpose of sequestration in this species as defence against predators. Through a series of prey choice experiments with three carabid predator species, chemically non-protected bark beetle pupae were chosen almost uniformly over L. anchusae pupae. In a following choice test with one of these predators, artificially PA-treated mealworm segments deterred the predator from feeding. Overall the study corroborates the immediate toxic effect of PAs on non-adapted herbivores and the protective effect that adapted insects may gain by sequestering them. It thereby underlines the potential for PAs to play a central role in multitrophic interactions between plants, phytophages and their predators.     

不同来源腐殖酸的光解及过氧化氢对其影响

为探讨腐殖酸在环境中的行为及光解除去腐殖酸的可能性，利用大于２９０ｎｍ的模拟日光辐照，探讨了大骨节病病区、非病区腐殖酸和泥炭腐殖酸的光解过程和光解机理及过氧化氢对其光解的影响，发现随着光照时间的延长，腐殖酸水体系的总有机碳（ＴＯＣ）含量降低，ｐＨ值下降，过氧化氢可以促进腐殖酸的光解，其光解过程遵循一级动力学规律。计算了不同来源腐殖酸光解的速率及光解半衰期，发现土壤和泥炭腐殖酸比大骨节病病区饮水中腐     

利用卫星数据估算波罗的海的透明度和透光层深度

波罗的海水体透明度的长期变化趋势已按富营养化的观点加以解释[1,2].可以通过遥感数据估算得到光谱衰减系数Kd(490)[3].由于漫衰减系数与透明度之间存在着经验和理论关系,因此,利用遥感数据估算海水营养状态是可能的.本文研究了遥感和水下实测Kd(490)与分别于1999年在东波罗的海本体海区[4]和2001年、2002年在西波罗的海本体海区/希默海区(Himmerfjarden)专门海上观测中获得的透明度之间的关系.利用水下测量值通过回归分析方法建立波罗的海PAR与光谱衰减系数间的关系.分析表明,在调查海区,Kd(490)约为Kd(PAR)的1.48倍.该关系用于定义透光层深度与遥感光学深度Kd(490)-1间的关系.结果表明,透光层深度约是Kd(490)-1的6.8倍.Kd(PAR)与透明度的回归分析结果证实了已有的研究结果,即Kd(PAR)为透明度倒数的1.7倍.再者,透明度与Kd(490)之间的水体成分反演算法用于模拟制作由SeaWiFS Kd(490)获得的波罗的海透明度分布图.该分布图通过海上实测数据加以验证,对卫星遥感获得的Kd(490)与实测Kd(490)做了对比,并讨论了产生误差的原因.     

Determination of atrazine in rainfall and surface water by enzyme immunoassay

Rainwater and surface water from four sites in Germany (Bavaria and Lower Saxony) were analyzed for atrazine by enzyme immunoassay from June 1990 until October 1992. The limit of quantification of the immunoassay was 0.02 μg/L with a middle of the test at 0.2 μg/L. About 60 % of the samples contained measurable amounts of atrazine. Seasonal trends were observed, with the highest concentration in the summer months of up to 4 μg/L for rainwater and up to 15 μg/L for surface waters. The highest concentrations were found in agricultural areas, while in the investigated national parks up to 0.56 μg/L could be detected in rain water. This points to long-range atmospheric transport from agricultural areas to pristine national parks. Samples from forest stands usually showed higher atrazine concentrations than samples from open fields. Deposition rates of 10 – 50 μg/m² · yr were observed in the national parks and 10–180 μg/m² · yr at the agricultural sites. Comparison of results obtained by enzyme immunoassay and GC/MS showed a good correlation of r = 0.95.     

Ligand exchange rate of metal-nom complexes by EDTA

Metal complexation by natural ligands is important for metal transport and distribution in surface and ground water. The goal of the work was to study the ligand exchange rate for two important metal ions in natural aquatic systems (Al, Fe) was determined using EDTA and natural organic matter (NOM) of humic type as ligands. After adding EDTA to a solution containing metal-NOM complexes, these complexes dissociated and metal-EDTA complexes were formed. Metal-NOM complexes were separated from metal-EDTA complexes with the help of size-exclusion chromatography and detected by on-line inductively coupled plasma-mass spectrometry (ICP-MS). Injecting the samples into the system over time after addition of EDTA allowed us to measure the rate of the exchange of NOM by EDTA. The experiments could be well described with a first-order rate law assuming that the dissociation of the metal-NOM complexes is the rate-determining step. The exchange rate of Fe was found to be faster than that of Al. This corresponds well with the exchange rate of water molecules from the coordination sphere of the metal ions, which is also faster for Fe than for Al. Furthermore, the UV and the fluorescence signal of the chromatograms were measured. The results indicate that no disaggregation of NOM molecules took place, although about 75-85% of the aggregate-forming metal ions exchanged NOM by EDTA in their coordination sphere. This suggests clearly the fundamental role of NOM in colloidal transport of metals and in their bioavailability.     

The transformation of outdoor ammonium nitrate aerosols in the indoor environment

Recent studies associate particulate air pollution with adverse health effects; however, the exposure to indoor particles of outdoor origin is not well characterized, particularly for individual chemical species. We conducted a field study in an unoccupied, single-story residence in Clovis, California to provide data and analyses to address issues important for assessing exposure. We used real-time particle monitors both outdoors and indoors to quantify nitrate, sulfate, and carbon particulate matter of particle size 2.5 μm or less in diameter (PM-2.5). The results show that measured indoor ammonium nitrate concentrations were significantly lower than would be expected based solely on penetration and deposition losses. The additional reduction can be attributed to the transformation indoors of ammonium nitrate into ammonia and nitric acid gases, which are subsequently lost by deposition and sorption to indoor surfaces. A mass balance model that accounts for the kinetics of ammonium nitrate evaporation was able to reproduce measured indoor ammonium nitrate and nitric acid concentrations, resulting in a fitted value of the deposition velocity for nitric acid of 0.56 cm s⁻¹. The results indicate that indoor exposure to outdoor ammonium nitrate in Central Valley of California are small, and suggest that exposure assessments based on total particle mass measured outdoors may obscure the actual causal relationships for indoor exposure to particles of outdoor origin.     

Biochemical response of Norway spruce (Picea abies (L.) karst.) towards 14-month exposure to ozone and acid mist: part II--Effects on protein biosynthesis

Four-year-old clonal Picea abies (L.) Karst. plants were treated with ozone (100 microm(-3) plus peaks of 130 to 360 microm(-3)) and acid mist (pH 3.0) during two vegetation periods. Pulse labelling experiments on shoots were performed with [(35)S]methionine in the second year of exposure. Extraction of soluble needle proteins in citric acid buffer of pH 2.8 revealed protein patterns on SDS polyacrylamide gels that differed from those of control needles fumigated with ambient levels of ozone (50 microg m(-3)) and mist of pH 5.6. New proteins of MW 16000 and 32000 were synthesized only in ozone-exposed needles and could not be detected in the controls.     

Nutritional correlates and mate acquisition role of multiple sexual traits in male collared flycatchers

The information content of a sexual signal may predict its importance in a multiple signal system. Many studies have correlated sexual signal expression with the absolute levels of nutrient reserves. In contrast, the changes of nutrient reserves associated with signal expression are largely unknown in the wild due to technical limitations although they are important determinants of signal information content. We compared two visual and eight acoustic sexual traits in male collared flycatchers to see whether the nutritional correlates of expression predict the role of the signal in sexual selection. We used single point assays of plasma lipid metabolites to estimate short-term changes in nutritional state in relation to sexual trait expression during courtship. As a measure of sexual selection, we estimated the relationship with pairing latency after arrival in a 4-year dataset. Males which found a mate rapidly were characterized by large wing and forehead patches, but small song strophe complexity and small figure repertoire size. Traits more strongly related to pairing latency were also more closely related to changes in nutrient reserves. This indicates a link between signal role and information content. Small wing patches and, surprisingly, complex songs seemed to indicate poor phenotypic quality and were apparently disfavoured at mate acquisition in our population. Future studies of the information content of sexual traits, especially dynamic traits such as song, may benefit from the use of plasma metabolite profiles as non-invasive indicators of short-term changes in body condition.     

Quantitative analysis of pyrrolizidine alkaloids sequestered from diverse host plants in Longitarsus flea beetles (Coleoptera, Chrysomelidae)

Summary. Several species of the flea beetles genus Longitarsus are able to sequester pyrrolizidine alkaloids (PAs) from their host plants. In five Longitarsus species we compare the concentration of PAs present in their host plants belonging to the Asteraceae or Boraginaceae with those found in the beetles. To get an estimate of the intrapopulation variability, three samples of five beetles each and five individual plants were analyzed for each comparison. A strong intrapopulation variability could be detected both among plant and beetle samples. The total concentration found in the beetles varied strongly between species. The local host plant and its phenology influence the concentrations present in the beetles as evidenced in comparisons of a single beetle species from two different hosts and of one beetle species collected at the same site at different times of the year. In addition, different beetle species apparently vary in their capacity to sequester the alkaloids, at the lowest extreme the mean PA concentration in the beetles (0.034 μg PA/mg dry weight) was 1/30 of the mean concentration found in the plant leaves (L. aeruginosus from Eupatorium cannabinum), at the highest extreme (2.098 μg PA/mg dw) the concentration in the beetles was a 1000 fold higher than in the plant leaves (L. nasturtii from Symphytum officinale). The highest mean concentration found in the beetles was 3.446 μg/mg dw (L. exoletus from Cynoglossum officinale). The absolute concentrations found in the beetles are comparable to other insects which have been shown to be effectively defended against their potential predators. Received 22 June 1999; accepted 25 August 1999     

Mikrobieller PAK-Abbau

The biodegradation of the five ring PAH benzo[a]pyrene (BaP) is assumed to be limited by the low water solubility of this compound. A mixed culture of microorganisms — isolated from a PAH-contaminated soil — was able to degrade¹⁴C labelled BaP in mineral medium by cometabolism with phenanthrene, fluoranthene, anthracene and pyrene as sources of carbon and energy. The mineralisation of these compounds to low levels resulted in an inhibition of the degradation of BaP. After the new addition of the four PAH compounds to the culture medium the mineralisation of BaP started again. A non-ionic surfactant of the alkylpolyglycoside type (Plantacare 2000 UP) increased the concentration of BaP in the culture medium because of solubilization. At high Plantacare concentrations, the degradation of BaP was completely inhibited above the critical micelle concentration (cmc). The degradation of the three and four ring PAHs was also inhibited. If the surfactant was metabolised to concentrations below the cmc, an increase of mineralisation of BaP could occur up to 24% in 384 days.