Assessing the organic composition of urban surface films using nuclear magnetic resonance spectroscopy

Recently it has been shown that urban surfaces are covered with a thin film which mediates the fate, distribution and accumulation of semi-volatile organic compounds in the environment. In this study we apply a combination of solution, semi-solids, and solid state nuclear magnetic resonance (NMR) methods to provide a general overview of the organic constituents. In surface film collected from 30 m2 of outside windows over an area of 12 km2 in downtown Toronto, we roughly estimate that the organic carbon is approximately 35% carbohydrate, approximately 35% aliphatics, approximately 20% aromatics, and approximately 10% carbonyl groups. Various aliphatic groups can be identified including a number of acids, alcohols, alkanes, and alkenes. Also, numerous intact aliphatic esters are apparent that have not been observed before, as well as carbohydrates. The aromatic species include a small portion that appears to be derived from a polymer of styrene, in addition a larger fraction is consistent with polyhydroxylated PAH derived material, although this assignment is tentative and based solely on 1-D NMR data only. In addition, signals from polybutadiene are present and while accurate quantification is not possible, it appears that this polymer may be up to a few percents by weight of the total organic material.     

The potential for kelp manufacture to lead to arsenic pollution of remote Scottish islands

Burning seaweed to produce kelp, valued for its high potash and soda content, was formerly a significant industry in remote coastal areas of Scotland and elsewhere. Given the high concentrations of arsenic in seaweeds, up to 100 mg kg(-1), this study investigates the possibility that the kelp industry caused arsenic contamination of these pristine environments. A series of laboratory-scale seaweed burning experiments was conducted, and analysis of the products using HPLC ICP-MS shows that at least 40% of the arsenic originally in the seaweed could have been released into the fumes. The hypothesis that the burning process transforms arsenic from low toxicity arsenosugars in the original seaweeds (Fucus vesiculosus and Laminaria digitata) to highly toxic inorganic forms, predominantly arsenate, is consistent with As speciation analysis results. A field study conducted on Westray, Orkney, once a major centre for kelp production, shows that elevated arsenic levels (10.7+/-3.0 mg kg(-1), compared to background levels of 1.7+/-0.2 mg kg(-1)) persist in soils in the immediate vicinity of the kelp burning pits. A model combining results from the burning experiments with data from historical records demonstrates the potential for arsenic deposition of 47 g ha(-1) year(-1) on land adjacent to the main kelp burning location on Westray, and for arsenic concentrations exceeding current UK soil guideline values during the 50 year period of peak kelp production.     

Global invasive potential of 10 parasitic witchweeds and related Orobanchaceae

The plant family Orobanchaceae includes many parasitic weeds that are also impressive invaders and aggressive crop pests with several specialized features (e.g. microscopic seeds, parasitic habits). Although they have provoked several large-scale eradication and control efforts, no global evaluation of their invasive potential is as yet available. We use tools from ecological niche modeling in combination with occurrence records from herbarium specimens to evaluate the global invasive potential of each of 10 species in this assemblage, representing several of the worst global invaders. The invasive potential of these species is considerable, with all tropical and subtropical countries, and most temperate countries, vulnerable to invasions by one or more of them.     

Foraging areas differentially affect reproductive output and interpretation of trends in abundance of loggerhead turtles

Diet items and habitat constitute some of the environmental resources that may be used differently by individuals within a population. Long-term fidelity by individuals to particular resources exemplifies individual specialization, a phenomenon that is becoming increasingly recognized across a wide range of species. Less is understood about the consequences of such specialization. Here, we investigate the effects of differential foraging ground use on reproductive output in 183 loggerhead sea turtles (Caretta caretta) nesting at Wassaw Island, Georgia (31.89°N, 80.97°W), between 2004 and 2011 with resulting possible fitness effects. Stable isotope analysis was used to assign the adult female loggerheads to one of three foraging areas in the Northwest Atlantic Ocean. Our data indicate that foraging area preference influences the size, fecundity, and breeding periodicity of adult female loggerhead turtles. We also found that the proportion of turtles originating from each foraging area varied significantly among the years examined. The change in the number of nesting females across the years of the study was not a result of uniform change from all foraging areas. We develop a novel approach to assess differential contributions of various foraging aggregations to changes in abundance of a sea turtle nesting aggregation using stable isotopes. Our approach can provide an improved understanding of the influences on the causes of increasing or decreasing population trends and allow more effective monitoring for these threatened species and other highly migratory species.     

Environmental fate of pesticides used in Australian viticulture III. Fate of dithianon from vine to wine

Pinot noir, bastardo, rkaziteli and semillon grapes on vines grown in the Barossa Valley of South Australia were treated with a commercial dithianon formulation. The grapes were harvested by hand eight days later, and made into wine. Grab samples of berries, grape juice and the young wine were analysed for fungicide residues. No dithianon was detected in control grape samples, grape juices or wines. Significant dithianon levels were detected on the skins of treated grape samples. Dithianon is stable on the surface of grapes under the ambient conditions prevalent under the grape canopy for at least two weeks. No dithianon was detected in grape juice, on grape skins after berry crushing, in the lees, or in the young wine. Dithianon is unstable in grape juice and wine. Dithianon half‐life (initial concentration = 1 μg/mL) in semillon grape juice = 2.8 h, semillon wine = 0.58 h, pinot noir grape juice = 4.6 h, and pinot‐noir wine = 0.29 h. Treatment with fining agents or heat does not significantly reduce the rate of degradation. These results suggest that spraying table grapes with dithianon two weeks before harvest would result in exposure to essentially the full dose of active ingredient sprayed, and increase the risk to human health through ingestion of this compound. However, any threat to human health from ingestion through grape juice or wine is limited since any contact with grape juice or wine leads to rapid decomposition of dithianon by some as yet undetermined process.     

Volume and financial value of species traded in the medicinal plant markets of Gauteng,South Africa

The demand for traditional medicinal plants and products in South Africa has created an extensive cross-border industry involving thousands of harvesters and traders. The market values of individual taxa vary considerably. Pricing structures fluctuate between markets and over time as the cost of harvesting species varies depending on a gatherer's access to the resources and the proximity of markets to the harvesting sites. This paper estimates trade values, describes the prices paid for 22 plant resources, investigates pricing structures relative to the mass/volume sold and the factors that influence the market price for plants. There is an inverse and disproportionate relationship between the price per kilogram (R/kg) and mass of the product sold. The smaller the quantity sold, the higher the R/kg sale values are relative to sales of larger quantities. This relationship is evident in different plant part types (e.g. bark and bulbs), species and markets (shops and street markets). Given the high mass sold relative to the price, bulbs, like bark, have the lowest R/kg values compared to other products like roots, fruits and leaves. The prices paid for heavier/denser species is thus disproportionate to the mass sold. If the relative values are used as an indicator of plant vulnerability (assuming high values indicate greater vulnerability), then bias is created in favour of 'lighter' and less dense plant parts typically sold in small quantities because of the nature of the plant part and the manner in which it is marketed and required by customers.     

Utilization of partially predated snail shells by the hermit crab Pagurus longicarpus Say, 1817

The hermit crab Pagurus longicarpus was shown to inhabit shells that were partially predated from intertidal areas of Long Island, New York. Among field collections of P. longicarpus, 2.13% of the hermit crabs (46 of 2155) were found with shells with snail tissue present. Over 90% of these partially predated snail shells were occupied by male hermit crabs. Although hermit crabs were in 8 species of snail shells, only Littorina littorea and Nassarius obsoletus were found occupied by hermit crabs and containing snail tissue. In the laboratory, we found that specimens of the spider crab Libinia emarginata were able to pull off the operculum of snails, leaving damage as found in field collections. In contrast, specimens of P. longicarpus were not able to prey on live, healthy snails. When specimens of P. longicarpus were placed in communal tanks, hermit crabs preferred partially predated snail shells to empty and original shells. However, original shells and empty shells were occupied with more frequency than partially predated shells when crabs were isolated. These findings indicate P. longicarpus actively seeks shells soon after attack and abandonment by snail predators, especially in the presence of competitors.     

Host selection by a kleptobiotic spider

Why do kleptobiotic spiders of the genus Argyrodes seem to be associated with spiders of the genus Nephila worldwide? Observations following introduction of experimental insect prey of different sizes and weights on to host webs revealed that: (1) small prey are more effectively retained on the web of Nephila clavipes than on the web of another common host, Leucauge venusta. (2) N. clavipes did not consume small prey that accumulated on the web whereas larger, heavier prey were enveloped and stored. (3) We observed clear partitioning of prey items between N. clavipes and Argyrodes spp.; diet selection by Argyrodes did not overlap with that of N. clavipes but closely overlapped with that of L. venusta. (4) L. venusta responds very quickly to prey impact whereas N. clavipes is slower, offering a temporal window of opportunity for Argyrodes foraging. (5) The ability of L. venusta to detect and respond to small items also means that it acts aggressively to Argyrodes spp., whereas N. clavipes does not. Consequently, food-acquisition behaviours of Argyrodes were clearly less risky with N. clavipes compared with L. venusta. We conclude that when a kleptobiotic organism has a choice of various host species, it will opt for the least risky host that presents the highest rate of availability of food items. The fact that Nephila species present such characteristics explains the worldwide association with Argyrodes kleptobiotic spiders.     

The role of Raman spectroscopy in the analytical chemistry of potable water

Advances in instrumentation are making Raman spectroscopy the tool of choice for an increasing number of chemical applications. For example, many recalcitrant industrial process monitoring problems have been solved in recent years with in-line Raman spectrometers. Raman is attractive for these applications for many reasons, including remote non-invasive sampling, minimal sample preparation and tolerance of water. To a lesser extent, Raman spectroscopy is beginning to play a significant role in environmental analysis for the same reasons. At present, the environmental applications typically apply only to the most contaminated situations due to the still relatively high limits of detection. However, some emerging sampling technologies hold out the promise that Raman may soon be more widely applicable to the analytical chemistry of potable water. Herein we discuss these recent advances, summarize some examples of environmental applications to aqueous systems and suggest avenues of future developments that we expect to be most useful for potable water analysis. Also, a simplified, but detailed, theory of normal Raman scattering is presented. While resonance-enhanced Raman spectroscopy, surface-enhanced Raman spectroscopy and non-linear Raman techniques are briefly discussed, their theories and instrumental configurations are not addressed. Also, this article deals primarily with the modern dispersive Raman experiment (as opposed to the Fourier transform Raman experiment), because it seems most suited for potable water analysis. The goal of this article is to give the environmental scientist with no specialized knowledge of the topic just enough theory and background to evaluate the utility of this rapidly developing analytical tool.