The effects of oil sands wetlands on wood frogs (Rana sylvatica)

Extraction of crude oil from oil sand produces solid (sand) and liquid (water with suspended fine particles) tailings materials, called oil sands process-affected materials (OSPM). These waste materials are stored on the mine site due to a “zero discharge” policy and must be reclaimed when operations end. The liquid tailings materials are known to contain naphthenic acids and polycyclic aromatic hydrocarbons and have high pH and salinity. One method of reclamation is the “wet landscape” approach, which involves using oil sands tailings materials to form wetlands that would mimic natural wetland ecological function. This study investigated the effects of wetlands formed with oil sands tailings materials on the survival and growth of wood frog (Rana sylvatica) larvae. In spring 2007, in-situ caging studies were completed in 14 wetlands that were of four different classes; young or old, reference or reclaimed. Tadpole survival was different between types of wetlands, with young tailings-affected wetlands (≤7 years old) having 41.5%, 62.6%, and 54.7% higher tadpole mortality than old tailings-affected (>7 years old), young reference, and old reference wetlands, respectively. Since old wetlands created from OSPM showed effects on tadpoles similar to those of reference wetlands, which had markedly lower toxicity than young tailings-affected wetlands, we provide evidence that wetlands, at least 7 years old, can sustain amphibian life.     

Investigation of bioremediation potential of zymogenous bacteria and fungi for crude oil degradation

Bioremediation potential of bacteria and fungi isolated from sludge samples has been investigated (Danube alluvium, Pančevo, Serbia). Total isolated microorganisms were divided into three parts. One part was added with actidione antifungicide. The second part was added with streptomycin antibiotic. The third part was without additives. Paraffinic type of crude oil was a substrate for assessment of bioremediation potential. The simulated oil biodegradation lasted 30, 60 and 90 days. Parallel with that, the experiments with blind trial were conducted. Extracts were isolated from the samples with chloroform in a separate funnel. They were assayed for the group composition (alkanes, aromatics, alcohols and fatty acids) by column chromatography. Alkane fraction was analysed by gas chromatography—mass spectrometry (GC–MS). The most intense oil degradation was achieved in the experiments with bacteria, somewhat weaker with consortium of fungi and bacteria, and the weakest bioremediation potential in these experiments was shown by fungi.     

Chemical mimicry in an incipient leaf-cutting ant social parasite

Some social parasites of insect societies are known to use brute force when usurping a host colony, but most use more subtle forms of chemical cheating either by expressing as few recognition cues as possible to avoid being recognized or by producing similar recognition cues to the host to achieve positive discrimination. The former “chemical insignificance” strategy represents a more general adaptive syndrome than the latter “chemical mimicry” strategy and is expected to be characteristic of early evolutionary stages of social parasitism. We tested this hypothesis by experimentally analyzing the efficiency by which Acromyrmex echinatior leaf-cutting ants recognize intruding workers of the incipient social parasite Acromyrmex insinuator. The results were consistent with the parasite being “chemically insignificant” and not with the “chemical mimicry” hypothesis. Gas chromatography–mass spectrometry analysis of cuticular hydrocarbon profiles showed that social parasite workers produce significantly fewer hydrocarbons overall and that their typical profiles have very low amounts of hydrocarbons in the “normal” C29–C35 range but large quantities of unusually heavy C43–C45 hydrocarbons. This suggests that the C29–C35 hydrocarbons are instrumental in normal host nestmate recognition and that the C43–C45 compounds, all of which are dienes and thus more fluid than the corresponding saturated compounds, may reinforce “chemical insignificance” by blurring any remaining variation in recognition cues.     

A pilot study on iodine in soils of Greater Kabul and Nangarhar provinces of Afghanistan

A robust and rapid methodology for the determination of iodine by inductively coupled plasma mass spectrometry in environmental samples is presented. Data were initially obtained for the validation of the analytical measurements, using 17 commercially available soil reference materials. The methodology was then tested on soil and water samples collected in Afghanistan where iodine deficiency and its effects are reportedly prevalent. Sample collections were conducted in Greater Kabul; the iodine in agricultural soils was determined to be in the range of 1.6–4.2 mg/kg and that in water drawn for drinking and irrigation was found to range from 9.9 to 22.7 μg/L. Samples were also collected in a second region, Nangarhar province, which is located to the east of Kabul, where goitres in the local population had been reported. The iodine content in soils and water at this location was 0.5–1.9 mg/kg and 5.4–9.4 μg/L, respectively. The organic content of soils in Kabul was found to be in the range of 1.9–4.2%; in Nangarhar, organic content ranged from 1.7 to 4.5%. All of the Afghan soils were slightly alkaline at pH 7.6–8.2.     

Determination trace amounts of copper, nickel, cobalt and manganese ions in water samples after simultaneous separation and preconcentration

In the present article, a simple, rapid, sensitive and economical method has been developed for the simultaneous separation and preconcentration of the trace amounts of copper, nickel, cobalt and manganese in water samples by using modified XAD-4 resins. The sorption was quantitative in the pH range 6.0–9.0, whereas quantitative desorption occurred instantaneously with 5.0 mL of 2 M HNO₃, and selected elements have been determined by using flame atomic absorption spectrometry. Dynamic ranges were 0.04–3.5, 0.1–6.0, 0.04–4.5 and 0.04–4.0 μg/mL for copper, nickel, cobalt and manganese, respectively. The detection limits were 9.2, 28.6, 12.3 and 5.7 ng/mL for Cu(II), Ni(II), Co(II) and Mn(II), respectively. The effects of the experimental parameters, including the sample pH, eluent type, interference ions and breakthrough volume, were studied for separation and preconcentration of Cu(II), Ni(II), Co(II) and Mn(II) ions. Determination of these ions in standard samples confirmed that the proposed method has good accuracy. The proposed method was used for the determination of these ions in water samples.     

伯胺N1923萃取一元有机酸的研究

考察了伯胺Ｎ１９２３对甲酸、乙酸、丙酸和丁酸以氯乙酸、二氯乙酸和三氯乙酸等一元有机酸的萃取、萃取反应属离子缔合机理,有机相中主要生成１：１的萃合物。探讨了有机酸种类、稀释剂性质、温度和无机盐等对萃取的影响。     

Field based speciation of arsenic in UK and Argentinean water samples

A field method is reported for the speciation of arsenic in water samples that is simple, rapid, safe to use beyond laboratory environments, and cost effective. The method utilises solid-phase extraction cartridges (SPE) in series for selective retention of arsenic species, followed by elution and measurement of eluted fractions by inductively coupled plasma mass spectrometry (ICP-MS) for “total” arsenic. The method is suitable for on-site separation and preservation of arsenic species from water. Mean percentage accuracies (n = 25) for synthetic solutions of arsenite (As^III), arsenate (As^V), monomethylarsonic acid (MA), and dimethylarsinic acid (DMA) containing 10 μg l⁻¹ As, were 98, 101, 94, and 105%, respectively. Data are presented to demonstrate the effect of pH and competing anions on the retention of the arsenic species. The cartridges were tested in the UK and Argentina at sites where arsenic was known to be present in surface and groundwaters, respectively, at elevated concentrations and under challenging matrix conditions. In Argentinean groundwater, 4–20% of speciated arsenic was present as MA and 20–73% as As^III. In UK surface waters, speciated arsenic was measured as 7–49% MA and 12–42% DMA. Comparative data from the field method using SPE cartridges and the laboratory method using liquid chromatography coupled to ICP-MS for all water samples provided a correlation of greater than 0.999 for As^III and DMA, 0.991 for MA, and 0.982 for As^V (P < 0.01).     

Sex pheromone of <Emphasis Type="Italic">Ectinus aterrimus</Emphasis> (L<Emphasis Type="SmallCaps">inné</Emphasis>, 1761) (Coleoptera: Elateridae)

Summary.   Ectinus aterrimus (L.) is a fairly common European click beetle species which develops mainly in forests. In pheromone gland extracts of female E. aterrimus, examined using gas chromatography – mass spectrometry (GC-MS), one single compound was present. This was identified as 7-methyloctyl 9-methyldecanoate by comparison with a synthetic sample. Field trapping trials revealed a highly significant attraction of male E. aterrimus towards this ester. The structure of the compound differs remarkably from the pheromones of the closely related Agriotes spp., which exclusively use terpene esters.     

Potential dietary effects on the fatty acid composition of the common jellyfish Aurelia aurita

Fatty acid composition of the natural and aquarium-reared common jellyfish Aurelia aurita was investigated. Fatty acid composition of the aquarium-reared A. aurita clearly reflected that of the diet, brine shrimp (Artemia). In the same way, fatty acid composition of the natural A. aurita was assumed to reflect those of natural diets. Samples of natural A. aurita were collected from April 1995 to September 1995 in the Seto Inland Sea, Japan, and their fatty acids were analyzed by gas chromatography and mass spectrometry. Variation of fatty acid compositions was seasonal rather than dependent on body size. Two major seasonal groups were divided by the cluster analysis of the A. aurita fatty acid composition: the April–June and the August–September clusters. The April–June cluster was characterized by high contents of the (n − 3)-fatty acids of diatom origin, accumulated via the grazing food chain. By contrast, the August–September cluster was characterized by an increase in (n − 6)-fatty acids of macroalgal origin, probably transferred via the detritus food chain. These results suggest that the diet of natural A. aurita may shift between the diatom-based food chain and the detritus-based food chain. Received: 12 April 2000 / Accepted: 1 December 2000     

Terminal double bonds in the alkenes and acetates of defensive secretion from the thrips Suocerathrips linguis Mound & Marullo, 1994 (Thysanoptera: Phlaeothripidae)

Defensive secretions of adult males and females of the subsocial thrips Suocerathrips linguis were examined using gas chromatography–mass spectrometry (GC–MS). The samples contained six long-chain acetates and five aliphatic alkanes and alkenes. Whole-body extracts yielded six methyl esters of fatty acids as well as hexadecyl acetate. Structures of the two main components, (11Z)-icosa-11,19-dienyl acetate and octadecyl acetate, were confirmed. The third most abundant substance was identified as octadec-17-enyl acetate, which is a new natural product. In addition, (9Z)-octadec-9-enyl acetate was identified along with other acetates. Pure icosadienyl acetate was found to remain liquid down to −15°C, and is the solvent for the solid components of the secretion cocktail. A tentative biosynthetic pathway for all of the 12 acetates, alkanes and alkenes is discussed, considering especially the components with terminal double bonds that are uncommon in Thysanoptera and other insects.     

Geochemistry of leachates from the El Fraile sulfide tailings piles in Taxco, Guerrero, southern Mexico

Leachates from the El Fraile tailings impoundment (Taxco, Mexico) were monitored every 2 months from October 2001 to August 2002 to assess the geochemical characteristics. These leachates are of interest because they are sometimes used as alternative sources of domestic water. Alternatively, they drain into the Cacalotenango creek and may represent a major source of metal contamination of surface water and sediments. Most El Fraile leachates show characteristics of Ca–SO₄, (Ca+Mg)–SO₄, Mg–SO₄ and Ca–(SO₄+HCO₃) water types and are near-neutral (pH=6.3–7.7). Some acid leachates are generated by the interaction of meteoric water with tailings during rainfall events (pH=2.4–2.5). These contain variable levels of SO₄ ²⁻ (280–29,500 mg l⁻¹) and As (<0.01–12.0 mg l⁻¹) as well as Fe (0.025–2352 mg l⁻¹), Mn (0.1–732 mg l⁻¹), Zn (<0.025–1465 mg l⁻¹) and Pb (<0.01–0.351 mg l⁻¹). Most samples show the highest metal enrichment during the dry seasons. Leachates used as domestic water typically exceed the Mexican Drinking Water Guidelines for sulfate, hardness, Fe, Mn, Pb and As, while acidic leachates exceed the Mexican Guidelines for Industrial Discharge Waters for pH, Cu, Cd and As. Speciation shows that in near-neutral solutions, metals exist mainly as free ions, sulfates and bicarbonates, while in acidic leachates they are present as sulfates and free ions. Arsenic appears as As^(V) in all samples. Thermodynamic and mineralogical evidence indicates that precipitation of Fe oxides and oxyhydroxides, clay minerals and jarosite as well as sorption by these minerals are the main processes controlling leachate chemistry. These processes occur mainly after neutralization by interaction with bedrock and equilibration with atmospheric oxygen.     

Transformations of <Emphasis Type="Italic">n</Emphasis>-alkanes from petroleum pollutants in alluvial groundwaters

Investigations presented in this paper were aimed at defining the alterations of n-alkane composition in cases of oil-polluted alluvial sediments. Therefore, oil-polluted groundwater samples, taken in five different time intervals during a period of 28 months, were investigated. Samples of alluvial sediments were taken from two boreholes within an oil refinery at Pancevo, Yugoslavia. In both boreholes significant alterations with characteristic degradation of "oil" n-alkanes with no odd- or even-member predominance were observed, as well as subsequent synthesis of new ones with pronounced even-member predominance, and with maxima at C₁₆ and C₁₈. Since no additional contamination of boreholes was observed by analyses of steranes and triterpanes, the observed changes can only be attributed to microbial activity. It is assumed that for the degradation of oil n-alkanes, as well as for the synthesis of "new" n-alkanes, algae such as dinoflagellates are responsible. This assumption was confirmed by identification of n-alcohols with even-member predominance (C₁₄–C₂₀), by identification of cholesterol, as well as of n-fatty acids with even-member predominance (C₁₄–C₁₈) in the extract with n-alkane even-member predominance. Electronic Publication     

Fecundity,brood loss and egg development through embryogenesis of <Emphasis Type="Italic">Armases cinereum</Emphasis> (Decapoda: Grapsidae)

The present work is a comprehensive study of reproduction and embryonic development of Armases cinereum. Ovigerous A. cinereum (Bosc, 1802) females from Sebastian Inlet, Florida (9.88–19.4 mm CW) lay 2,000–12,000 eggs per brood, depending on their CW (mm): fecundity = 24.662 CW^1.9432. A. cinereum displayed significant brood loss through development (ca. 500 eggs per brood) independently from their CW (no senescence). However, since smaller females lay fewer eggs than larger ones, the percentage of eggs lost during embryonic development is greater in smaller females. The number of eggs carried on a later stage of development (potential fertility = 5.5593 CW^2.4417) is a more accurate estimate of the reproductive output and subsequent recruitment. Egg volume increased during development (64%, 0.025–0.041 mm³ or 0.36–0.43 mm of diameter, N = 270) and was strongly correlated with egg water content increase (19.21%, r = 0.89). Lipids, particularly fatty acids, seem to be the major energy source for embryonic development, decreasing 56.31 and 37.08% (respectively) during embryonic development; both are negatively correlated with egg volume (r = −0.90). The utilization of fatty acids through the different developmental stages of A. cinereum is presented. The most consumed fatty acids are the monounsatured (43.33 μg mg⁻¹ dw), followed by the saturated (29.91 μg mg⁻¹ dw) and polyunsaturated (24.03 μg mg⁻¹). Palmitic (16:0) and linoleic (18:2n-6) acids are preferentially consumed (19.5 and 17.9 μg mg⁻¹ dw, respectively). The high proportion of essential polyunsaturated fatty acids of C₁₈ and C₂₀ reflects the consumption of primary producers such as mangrove leaves. EPA/DHA ratio (2.85–3.84) and low DHA content indicated that this species appears in a medium-low level of the trophic chain. The low ratio of 18:1n-7/18:1n-9 and high percentage of 18:1n-9 (marker of carnivory) may be a sign of the consumption of juvenile invertebrates. The high percentage of odd-numbered FA indicated the occurrence of detritivores/scavenger behaviours. The fatty acid composition of the eggs reflects adult feeding ecology (omnivorous) and habitat.     

Kinetics of glucose and amino acid uptake by attached and free-living marine bacteria in oligotrophic waters

Kinetics of glucose and amino acid uptake by attached and free-living bacteria were compared in the upper 70 m of the oligotrophic north-western Mediterranean Sea. Potential uptake rates of amino acids were higher than those of glucose in all the samples analysed. Cell-specific potential uptake rates of attached bacteria were up to two orders of magnitude higher than those of total bacteria, both for amino acids and glucose (0.72–153 amol amino acids cell⁻¹ h⁻¹ and 0.05–58.42 amol glucose cell⁻¹ h⁻¹ for attached bacteria and 0.34–1.37 amol amino acids cell⁻¹ h⁻¹ and 0.07–0.22 amol glucose cell⁻¹ h⁻¹ for total bacteria). The apparent K _m values were also higher in attached bacteria than in total bacteria, both for amino acids and glucose. These results would reflect the presence of different uptake systems in attached and free-living bacteria, which is in accordance with the different nutrient characteristics of their microenvironments, ambient water and particles. Attached bacteria show transport systems with low affinity, which characterise a bacterial community adapted to high concentration of substrates. Received: 13 June 2000 / Accepted: 6 December 2000     

Selenium Distribution in Topsoils and Plants of a Semi-arid Mediterranean Environment

Selenium was determined from 25 topsoils and 25 plants in the semi-arid Central Spain where large extents of soils are developed on evaporitic materials. Some species of vegetation associated with them are of the genera Astragalus, Salsola, Mercurialis, Phlomis, Thymus and Atriplex. Total selenium in soils was determined and its bioavailability assessed by chemical sequential fractionation. Se content in soils was adequate (in the range 0.17–0.39 mg kg⁻¹) or large (in the range 0.50–4.38 mg kg⁻¹) and appeared in highly and/or potentially available forms. Several plant species showed high Se levels (in the range 5–14.3 mg kg⁻¹), which can be a potential risk of toxicity to animals. Data obtained from the study area can be used as a guide to the range of values in soils and plants of the European Mediterranean area that are relatively unpolluted from industrial sources, allowing comparison with more polluted areas.     

Electrophysiological responses of four fungivorous coleoptera to volatiles of Trametes versicolor: implications for host selection

Fungi of the genus Trametes are known as important wood decomposers and are colonized by various species of Coleoptera and other arthropods. The aim of the present study was to investigate the importance of volatile chemical compounds as key attraction factors in recognition and host selection by species of Erotylidae (Dacne bipustulata, Tritoma bipustulata) as well as Cisidae (Sulcacis affinis) and Tenebrionidae (Diaperis boleti). Volatiles from freshly collected Trametes versicolor were collected by headspace sampling technique and identified by combined gas chromatography–mass spectrometry (GC–MS). To evaluate the biological significance of the volatiles we performed behavioural tests and recorded antennal responses of the fungus-inhabiting species by gas chromatography with electroantennographic detection (GC-EAD). The scent of T. versicolor was found to be dominated by sesquiterpenes; in GC-EAD 6 of these compounds elicited reproducible antennal signals in the tested species. Highly significant attraction effects to the fungus, the obtained odour samples and previously described fungal C₈-compounds were observed in behavioural tests. The possibility to detect these chemical compounds as a key cue for host selection implicate that beetles are able to discriminate between fungi of different age as well as different stages of colonization.     

Persistence of gemfibrozil, naproxen and mefenamic acid in natural waters

The occurrence of pharmaceuticals in natural waters is a potential threat to human nutrition and ecosystem quality. The persistence of the acidic pharmaceuticals gemfibrozil, naproxen and mefenamic acid was studied in surface waters of Maracaibo Lake and Tule reservoir (Venezuela) under laboratory conditions. A quick and easy analytical method was developed for the determination of the acidic drugs at microgram per liter levels using aqueous derivatization, liquid–liquid extraction and gas chromatography–mass spectrometry. Pharmaceuticals degradation followed a pseudo first-order kinetic and their half-lives were calculated for every experimental condition. Under sunlight, naproxen and mefenamic acid were degraded at moderate rates with half-lives from 9.6 ± 0.5 to 27.0 ± 6.6 days, while gemfibrozil had a higher persistence (t _1/2 = 119.5 ± 15.6 − 288.8 ± 61.3 days).     

Patterns of organic osmolytes in two marine bivalves, Macoma balthica, and Mytilus spp., along their European distribution

Patterns of nine intracellular free amino acids (FAA), which are utilized as organic osmolytes for salinity-induced cell volume regulation in marine osmoconformers, were compared in five Macoma balthica populations and seven Mytilus spp. populations along their European distribution. Three types of FAA patterns were classified within both taxa: a northern Baltic type, a southern Baltic type and an Atlantic/Mediterranean type which mainly differ regarding the share of alanine and taurine. Differences are discussed in relation to habitat salinity and population genetics. Along a salinity gradient, the total size of the intracellular FAA pool did not differ between sympatric M. balthica and Mytilus spp., and was significantly correlated with habitat osmolality in a range from 70 to 600 mmol kg⁻¹ H₂O (oligohaline to mesohaline) in both bivalves. In M. balthica, this correlation was mainly based on significant correlations of alanine (15–100 mmol kg⁻¹ DW), glycine (30–100 mmol kg⁻¹ DW) and taurine (0–70 mmol kg⁻¹ DW) with habitat osmolality. In Mytilus spp., only glycine (25–100 mmol kg⁻¹ DW) and taurine (4–180 mmol kg⁻¹ DW) were significantly correlated with habitat osmolality. The concentration of alanine was three times lower in Mytilus spp. than in M. balthica and did not correlate with habitat osmolality. Within a habitat osmolality range from 600 to 1,100 mmol kg⁻¹ H₂O (mesohaline to marine) the concentration of FAA remained constant in both taxa. It is suggested that under marine conditions additional organic osmolytes must become more important for cell volume regulation in Macoma and Mytilus.     

Larval growth and settlement of the European oyster (Ostrea edulis) as a function of food quality measured as fatty acid composition

Larval growth rate and settlement of the European flat oyster Ostrea edulis were experimentally studied as a function of the composition of dietary fatty acids. Diets differing in fatty acid composition were composed by mixtures of the microalgae Isochrysis galbana, Pavlova lutheri and Chaetoceros calcitrans. Fatty acid content in the tissue of the feeding larvae, analyzed by gas chromatography and mass spectrometry, reflected the composition in the diet. Larval growth rate was significantly correlated to the three omega-3 polyunsaturated fatty acids (PUFA) C18:3, C18:4 and C22:6, with minor differences for neutral and polar lipids. No relation between growth rate and the omega-3 PUFA C20:5 was detected, a PUFA often implied as essential for bivalves. It is suggested that naturally occurring variability in fatty acid composition may constrain larval growth. In settlement experiments in both still water and flume flow little substrate selectivity was found for some contrasting substrates. It is concluded that differences in dietary fatty acids may explain as much of settlement success as the variability of substrates. Received: 12 October 1998 / Accepted: 6 April 1999     

Effects of ocean acidification on invertebrate settlement at volcanic CO2 vents

We present the first study of the effects of ocean acidification on settlement of benthic invertebrates and microfauna. Artificial collectors were placed for 1 month along pH gradients at CO₂ vents off Ischia (Tyrrhenian Sea, Italy). Seventy-nine taxa were identified from six main taxonomic groups (foraminiferans, nematodes, polychaetes, molluscs, crustaceans and chaetognaths). Calcareous foraminiferans, serpulid polychaetes, gastropods and bivalves showed highly significant reductions in recruitment to the collectors as pCO₂ rose from normal (336–341 ppm, pH 8.09–8.15) to high levels (886–5,148 ppm) causing acidified conditions near the vents (pH 7.08–7.79). Only the syllid polychaete Syllis prolifera had higher abundances at the most acidified station, although a wide range of polychaetes and small crustaceans was able to settle and survive under these conditions. A few taxa (Amphiglena mediterranea, Leptochelia dubia, Caprella acanthifera) were particularly abundant at stations acidified by intermediate amounts of CO₂ (pH 7.41–7.99). These results show that increased levels of CO₂ can profoundly affect the settlement of a wide range of benthic organisms.