On-line dechlorination–hydrogenation of chlorinated paraffin mixtures using GC and GC/MS

Chlorinated paraffins (CPs) are straight chain hydrocarbons that are produced as complex mixtures and are used as flame retardants and paint additives. These mixtures are extremely difficult to characterize using conventional chromatographic methods, as conventional gas chromatography results in unresolved complex chromatograms that preclude the identification and quantification of individual congeners or any reasonable assessment of the average carbon chain length. Carbon chain length is an important parameter for assessing physical properties and the toxicity of these materials. We have modified and improved a previously published gas chromatography–flame ionization detector method that uses Pd catalyst held in the gas chromatograph injector to simultaneously dechlorinate the CPs and separate the resulting alkanes. In addition, we have adapted this method to gas chromatography–mass spectrometry. Dehalogenation of other compounds was also studied with this system to investigate potential application to other complex halogenated mixtures.     

Application of Adjoint Approach to Oil Spill Problems

Adjoint method is applied to various oil spill problems. A three-dimensional model for describing the dispersion of a quasi-passive substance (a pollutant or a nutrient) and its adjoint model are considered in a limited sea region. Direct and adjoint estimates are used to get dual (equivalent) estimates of the mean concentration of the substance in important zones of the region. The role of dual estimates is illustrated with a few examples. They include such oil spill problems as the search of the most dangerous point of the oil tanker route, the oil dispersion with a climatic velocity, and the dependence of the oil concentration estimates on the oil spill rate. One more example is the application of optimal bioremediation strategy for cleaning a few zones polluted by oil. In this case, instead of oil, the model describes the dispersion of a nutrient released to marine environment. Balanced, unconditionally stable second-order finite-difference schemes based on the splitting method for the solution of the dispersion model and its adjoint are suggested. The main and adjoint difference schemes are compatible in the sense that at every fractional step of the splitting algorithm, the one-dimensional split operators of both schemes satisfy a discrete form of Lagrange identity. In the special unforced and non-dissipative case, each scheme has two conservation laws. Every split one-dimensional problem is solved by Thomas’ factorization method.     

Production of Curdlan Grown on Cassava Starch Waste Hydrolysates

Cassava starch waste hydrolysates (CSWHs) with different degrees of polymerisation, i.e., CSWHs-1, CSWHs-2 and CSWHs-3, were prepared through the hydrolysis of cassava starch waste with thermostable a-amylase from Thermococcus sp. HJ21. The prepared CSWHs were then used as a carbon source for curdlan production with Alcaligenes faecalis ATCC 31749. The amount of curdlan produced and the glucosyltransferase activity during curdlan synthesis increased more obviously when CSWHs-2 was used as the carbon source than when glucose was used. Using both carbon sources, the maximum curdlan production was observed at day 5, and the maximum glucosyltransferase activity was observed at day 4. Glucosyltransferase activity decreased thereafter, and biomass continued to increase until the end of the experiment (day 6). Results indicated that the enhanced curdlan production with CSWHs as the carbon source was highly correlated with glucosyltransferase activity.     

Evaluating day–night changes in shallow Mediterranean rocky reef fish assemblages by visual census

Ecological information on coastal fish distribution patterns and habitat use can be greatly improved by nocturnal samplings and observations. To this purpose, the structure of a Mediterranean fish assemblage inhabiting the shallow rocky littoral of Linosa Island (Sicily Strait, Italy) was examined by using visual census to detect possible diel variations in species composition and abundance. Day–night fish distribution patterns were investigated by multivariate and univariate analyses. Overall, 42 fish taxa belonging to 19 families were recorded: 35 during the day and 24 during the night. Seventeen species were common to both diurnal and nocturnal assemblages. Within the diurnal assemblage, Chromis chromis was the most represented species (37.2%), followed by Thalassoma pavo (23.2%) and Sparisoma cretense (10.8%). Within the nocturnal assemblage, the most abundant taxon was Atherina spp. (33.9%), followed by Apogon imberbis (26.4%) and Boops boops (11.5%). Our results indicated wide variation in the abundance and species composition during the day and during the night. Multi Dimensional Scaling plot showed a clear-cut separation between the two assemblages and analysis of similarities found significant differences as well. SIMPER analysis revealed that ten species individually contributed by more than 2.5% to the dissimilarity between diurnal and nocturnal assemblages, T. pavo, C. chromis and S. cretense being the first three species in order of decreasing percentage. ANOVA performed on species richness and fish abundance detected significant differences between diurnal and nocturnal assemblages, the latter showing far lower average values for both variables.     

The effect of salinity on survival,bioenergetics and predation risk in the mud crabs <Emphasis Type="Italic">Panopeus simpsoni</Emphasis> and <Emphasis Type="Italic">Eurypanopeus depressus</Emphasis>

The effect of salinity on survival, bioenergetics and predation risk was studied in two common mud crabs in the Gulf of Mexico, Eurypanopeus depressus and Panopeus simpsoni. Eurypanopeus survived better at low salinities (the 28-day LC₅₀ of E. depressus was 0.19 PSU compared with 6.97 PSU for P. simpsoni). While low salinity increased energy expenditure and reduced food consumption and absorption, resulting in lower scope for growth, identical responses to salinity occurred in both species. Both species also had similar salinity-dependent patterns of hyper-osmoregulation. Because these physiological mechanisms could not explain differences between the two species in salinity tolerance, we explored the effect of salinity on competition for refugia. Eurypanopeus had higher resource holding potential for refugia, especially at low salinity. As a consequence it had lower predation risk to blue crabs in laboratory experiments. The higher tolerance by E. depressus for low salinities, and greater resource holding potential for refugia may explain why it has a more euryhaline distribution than P. simpsoni.     

Signals for damage control: web decorations in <Emphasis Type="Italic">Argiope keyserlingi</Emphasis> (Araneae: Araneidae)

Orb web spiders of the genus Argiope are permanently located at the hub of the orb web and are thus vulnerable to changing environmental conditions. Severe damage to the web by non-prey animals can have a significant impact on survival, through the cost of producing expensive silk and the loss of foraging opportunities. Thus, selection should favor web protection mechanisms, and the conspicuous web decorations, typical of Argiope spiders, may play a role. Decorated webs suffer less damage than undecorated webs, consistent with the view that they advertise the presence of the web to non-prey animals that may damage the web. However, whether spiders respond to web damage by increasing investment in web decorations has not been investigated. We subjected adult St. Andrew's Cross spider (Argiope keyserlingi) females to three levels of web damage and recorded their subsequent web-decorating behavior. Mild damage, similar to that caused by impacting prey, did not affect either web building or decorating behavior. However, spiders subjected to substantial web damage both reduced the size of subsequent webs and increased investment in web decoration size. These data are consistent with an advertising role of web decorations.     

Feeding on intertidal microbial mats by postlarval tiger shrimp, <Emphasis Type="Italic">Penaeus semisulcatus</Emphasis> De Haan

A series of experiments investigated the potential role of microbial mats in nutrition of the early settlement stages of Penaeus semisulcatus. From 3 days post-metamorphosis, the microbial mat supported high growth and survival rates in postlarvae, equivalent to that supported by a control diet of Artemia nauplii and mussel. Examination of gut contents indicated that benthic postlarvae feed indiscriminately on the microbial mat. However, when postlarvae were fed separated size-fractions of the microbial mat, only the fraction containing a high concentration of infauna (mainly nematodes) was able to support the same growth as intact microbial mat. This appears to be due to the low nitrogen content (0.4–0.9 mmol g⁻¹) of the various size-fractions, compared to that of infauna (4.0 mmol g⁻¹). The stable isotope composition of the dietary size-fractions and postlarval shrimp tissue supports the hypothesis that the shrimp assimilated C and N primarily from the associated infauna. This may be due to selective feeding that is not apparent from stomach contents, due to rapid digestion of fauna soft tissues, or to differential assimilation of infaunal prey relative to other microbial mat components. The results demonstrate that microbial mats may support survival and growth in early-stage penaeid shrimp postlarvae on intertidal mud flats.     

Cyclodextrin-based supramolecular assemblies: a versatile toolbox for the preparation of functional porous materials

The discovery of ordered mesoporous materials in 1992 by Mobil Oil Corporation scientists has opened great opportunities for new applications in many emerging fields such as heterogeneous catalysis, biocatalysis, energy conversion, biosensors, photocatalytic devices and environmental technologies. Porous materials are grouped by the International Union of Pure and Applied Chemistry (IUPAC) into three classes according to their pore diameter: microporous (<?2 nm), mesoporous (2–50 nm) and macroporous (>?50 nm). One of the most versatile methods for the preparation of those materials is the soft template approach which combines the sol–gel process with molecular self-assembly. While the micelles formed by ionic or nonionic surfactants, as well as amphiphilic polymers, have been extensively used as templates, the supramolecular assemblies formed between cyclodextrins and block copolymers have been less investigated, despite their large chemical and structural diversity. This review article focuses mainly on nanostructured porous inorganic materials derived from cyclodextrins or cyclodextrin-based assemblies. More than 100 references are described and discussed, in which we look both at their synthesis and characterization, as well as their applications in the emerging fields of heterogeneous catalysis and photocatalysis. A special attention is paid to the evaluation of the critical parameters that need to be controlled for improving their (photo) catalytic performances.     

Arsenic,antimony, and other trace element contamination in a mine tailings affected area and uptake by tolerant plant species

The study was conducted to characterize mineralogical and elemental composition of mine tailings in order to evaluate the environmental hazards, and identify the metal accumulation potential of native plant species from São Domingos mine, one of the long-term activity mines of the Iberian Pyrite Belt dating back to pre-Roman times. The mine tailings including soils and different plant species from São Domingos were analyzed for determination of tailings characteristics and chemical element contents in tailings and plants. The large amounts of mining wastes are causing significant adverse environment impacts due to acid mine drainage production and mobilization of potentially toxic metals and metalloids in residential areas, agricultural fields, downstreams, and rivers. The typical mineralogical composition is as follows: quartz, micas, K-feldspar, olivine-group minerals, magnetite, goethite, hematite, jarosite, and sulfides. The mine tailings were highly contaminated by As, Ag, Cr, Hg, Sn, Sb, Fe, and Zn; and among them, As and Sb, main contaminants, attained the highest concentrations except Fe. Arsenic has exhibited very good correlations with Au, Fe, Sb, Se, and W; and Sb with As, Au, Fe, Se, Sn, and W in tailings. Among the all plant species, the higher concentrations of all the metals were noted in Erica andevalensis, Erica australis, Echium plantagium, and Lavandula luisierra. Considering the tolerant behavior and abundant growth, the plant species Erica australis, Erica andevalensis, Lavandula luisierra, Daphne gnidium, Rumex induratus, Ulex eriocladus, Juncus, and Genista hirsutus are of major importance for the rehabilitation and recovery of degraded São Domingos mining area.     

Phytoextraction of lead-contaminated soil using vetivergrass (<Emphasis Type="Italic">Vetiveria zizanioides</Emphasis> L.), cogongrass (<Emphasis Type="Italic">Imperata cylindrica</Emphasis> L.) and carabaograss (<Emphasis Type="Italic">Paspalum conjugatum</Emphasis> L.)

Background, Aims and Scope The global problem concerning contamination of the environment as a consequence of human activities is increasing. Most of the environmental contaminants are chemical by-products and heavy metals such as lead (Pb). Lead released into the environment makes its way into the air, soil and water. Lead contributes to a variety of health effects such as decline in mental, cognitive and physical health of the individual. An alternative way of reducing Pb concentration from the soil is through phytoremediation. Phytoremediation is an alternative method that uses plants to clean up a contaminated area. The objectives of this study were: (1) to determine the survival rate and vegetative characteristics of three grass species such as vetivergrass, cogongrass and carabaograss grown in soils with different Pb levels; and (2) to determine and compare the ability of the three grass species as potential phytoremediators in terms of Pb accumulation by plants. Methods The three test plants: vetivergrass (Vetiveria zizanioides L.); cogongrass (Imperata cylindrica L.); and carabaograss (Paspalum conjugatum L.) were grown in individual plastic bags containing soils with 75 mg kg⁻¹ (37.5 kg ha⁻¹) and 150 mg kg⁻¹ (75 kg ha⁻¹) of Pb, respectively. The Pb contents of the test plants and the soil were analyzed before and after experimental treatments using an atomic absorption spectrophotometer. This study was laid out following a 3 × 2 factorial experiment in a completely randomized design. Results On the vegetative characteristics of the test plants, vetivergrass registered the highest whole plant dry matter weight (33.85–39.39 Mg ha⁻¹). Carabaograss had the lowest herbage mass production of 4.12 Mg ha⁻¹ and 5.72 Mg ha⁻¹ from soils added with 75 and 150 mg Pb kg⁻¹, respectively. Vetivergrass also had the highest percent plant survival which meant it best tolerated the Pb contamination in soils. Vetivergrass registered the highest rate of Pb absorption (10.16 ± 2.81 mg kg⁻¹). This was followed by cogongrass (2.34 ± 0.52 mg kg⁻¹) and carabaograss with a mean Pb level of 0.49 ± 0.56 mg kg⁻¹. Levels of Pb among the three grasses (shoots + roots) did not vary significantly with the amount of Pb added (75 and 150 mg kg⁻¹) to the soil. Discussion Vetivergrass yielded the highest biomass; it also has the greatest amount of Pb absorbed (roots + shoots). This can be attributed to the highly extensive root system of vetivergrass with the presence of an enormous amount of root hairs. Extensive root system denotes more contact to nutrients in soils, therefore more likelihood of nutrient absorption and Pb uptake. The efficiency of plants as phytoremediators could be correlated with the plants’ total biomass. This implies that the higher the biomass, the greater the Pb uptake. Plants characteristically exhibit remarkable capacity to absorb what they need and exclude what they do not need. Some plants utilize exclusion mechanisms, where there is a reduced uptake by the roots or a restricted transport of the metals from root to shoots. Combination of high metal accumulation and high biomass production results in the most metal removal from the soil. Conclusions The present study indicated that vetivergrass possessed many beneficial characteristics to uptake Pb from contaminated soil. It was the most tolerant and could grow in soil contaminated with high Pb concentration. Cogongrass and carabaograss are also potential phytoremediators since they can absorb small amount of Pb in soils, although cogongrass is more tolerant to Pb-contaminated soil compared with carabaograss. The important implication of our findings is that vetivergrass can be used for phytoextraction on sites contaminated with high levels of heavy metals; particularly Pb. Recommendations and Perspectives High levels of Pb in localized areas are still a concern especially in urban areas with high levels of traffic, near Pb smelters, battery plants, or industrial facilities that burn fuel ending up in water and soils. The grasses used in the study, and particularly vetivergrass, can be used to phytoremediate urban soil with various contaminations by planting these grasses in lawns and public parks. ESS-Submission Editor: Dr. Willie Peijnenburg (wjgm.peijnenburg@rivm.nl)