Relevance of enantiomeric separations in environmental science

A significant number of all organic chemicals that are released into the environment are racemic mixtures. Most environmental regulations and scientific environmental studies treat racemic mixtures as though they were single, pure compounds. This can lead to incorrect toxicological, distribution, degradation and other data. A series of new enantioselective chromatographic techniques have been developed that allow the facile separation and quantitation of chiral compounds of environmental importance. Nineteen racemic compounds that have been or currently are being released to the environment are resolved. These include: rodenticides--Warfarin, Coumachlor and Coumafuryl; insecticides--Crufomate, Bulan, Fonofos, Mitotane; insect repellent--Ethohexadiol; herbicides and fungicides--Ancymidol, Silvex, Napropamide, phenyl mercuric lactate, 2-[3-chlorophenoxy]propionamide, and 2-chloropropionic acid; and halocarbons-1,2-dichloropropane, 2-bromo-1-chloropropane, 1,2-dibromo-3-chloropropane, 2,3-dichlorobutane and alpha-1,2,3,4,5,6-hexachlorocyclohexane. Several examples are given to illustrate the importance of enantioselective measurements of these and other compounds. Choosing the proper chromatographic technique and chiral stationary phase based on analyte structure is also discussed.     

Variations in the abundance of Centropages typicus and Calanus helgolandicus in the North Sea: deviations from close relationships with temperature

The interannual variations in abundance of the calanoid copepod Centropages typicus (Krøyer) in the North Sea are significantly positively correlated with sea-surface temperature. The same is true of Calanus helgolandicus Claus. In both cases there was a deviation from the close relationship with temperature for several years in the early to mid-1980s. Centropages typicus was less abundant than expected from 1981 to 1984, but Calanus helgolandicus recovered from a period of lower than expected abundance from 1980 to 1982, to become more abundant than expected from 1983 to 1987. The difference between the responses of the two species to climate-driven changes in seasonal cycles of phytoplankton is interpreted in relation to their biology. Geographical variations of the interannual variability and seasonal cycles of Centropages typicus in the North Sea are analysed. The centre of the population of this species in the North Sea is in the German and Southern Bights, but the variations in abundance may be partly influenced by advection from areas to the west of Britain.     

Distribution and diet of juvenile Patagonian toothfish on the South Georgia and Shag Rocks shelves (Southern Ocean)

The distribution and diet of juvenile (<750 mm) Patagonian toothfish are described from four annual trawl surveys (2003–2006) around the island of South Georgia in the Atlantic sector of the Southern Ocean. Recruitment of toothfish varies inter-annually, and a single large cohort dominated during the four years surveyed. Most juveniles were caught on the Shag Rocks shelf to the NW of South Georgia, with fish subsequently dispersing to deeper water around both the South Georgia and Shag Rocks shelves. Mean size of juvenile toothfish increased with depth of capture. Stomach contents analysis was conducted on 795 fish that contained food remains and revealed that juvenile toothfish are essentially piscivorous, with the diet dominated by notothenid fish. The yellow-finned notothen, Patagonotothen guntheri, was the dominant prey at Shag Rocks whilst at South Georgia, where P. guntheri is absent, the dominant prey were Antarctic krill and notothenid fish. The diet changed with size, with an increase in myctophid fish and krill as toothfish grow and disperse. The size of prey also increased with fish size, with a greater range of prey sizes consumed by larger fish.     

The co-application of earthworms (Dendrobaena veneta) and compost to increase hydrocarbon losses from diesel contaminated soils

The feasibility of using composted civic waste for the remediation of a soil contaminated with petroleum hydrocarbons (extractable petroleum hydrocarbons (EPH) 10+/-1.8 g kg(-1) and total 16 USEPA PAH 1.62+/-0.5 g kg(-1)) was assessed. The effects of compost to soil ratio, in combination with and without earthworm presence (Dendrobaena veneta), upon the loss of contaminants were determined for EPH (GC-FID) and PAH (GC-MS), respectively. Increasing the ratio of compost substrate to hydrocarbon impacted soil (1:0.5, 1:1, 1:2 and 1:4 (soil:compost wt/wt)) in the absence of earthworms resulted in significantly (p<0.05) greater losses of both EPH and SigmaPAH after an 84 d incubation period, when compared to the soil only control. Where earthworms were present without compost, EPH losses were significantly (p<0.05) enhanced in the soil only treatment (33.4+/-5.3% residual) compared to the soil only control (54.4+/-5.3% residual). However, PAH loss in the soil only treatment (with-earthworm presence) were only slightly enhanced (65.3+/-9.3% residual), with respect to the soil only control (69.2+/-6.4% residual). Synergistic benefits of both earthworm and compost presence were most significant for PAHs (p<0.05), and less so for EPH. (14)C-respirometer studies, to establish catabolic competence in terms of microbial mineralisation of key hydrocarbons, complemented the hydrocarbon analysis.     

Life cycle assessment of mine tailings management in Canada

The effective management of mine tailings involves the control of several environmental impacts and legal requirements. Six tailings site management and closure scenarios were developed for a copper zinc underground mine located in Quebec (Canada) and compared using life cycle assessment (LCA). Two options are considered for the mine operation: tailings can be sent to the tailings disposal area where they are submerged or they can be partly used for backfilling. For each of these two operation options, three alternatives are presented for mine closure: (a) submerged tailings, (b) partial desulphurization with a cover of desulphurized material and (c) a cover with capillary barrier effects (CCBE) made of natural soils followed by revegetation. The goals of the study were to draw the inventory of these management scenarios from the development to the post-closure phase, to assess and compare their environmental impacts and to determine the importance of the land-use impact category. The potential impacts for each scenario were evaluated using the IMPACT 2002+ LCIA method. The results of the performed LCA indicate that for mine development and operation, scenarios where tailings are partly used as backfill for underground stopes appear to lead to larger impacts in 11 of the 14 midpoint categories since the backfill plant operation consumes a greater amount of material and energy. For a site closure period of 2 years, the CCBE option creates the greatest impacts, since it requires much more effort than the other techniques. The results for the post-closure phase have been analysed separately since they have a larger uncertainty. They appear to modify the comparative assessment results. The various results presented in the paper show the importance of taking land-use impacts into account.     

A passive air sampler for characterizing the vertical concentration profile of gaseous phase polycyclic aromatic hydrocarbons in near soil surface air

Air-soil exchange is an important process governing the fate of polycyclic aromatic hydrocarbons (PAHs). A novel passive air sampler was designed and tested for measuring the vertical concentration profile of 4 low molecular weight PAHs in gaseous phase (PAH_LMW4) in near soil surface air. Air at various heights from 5 to 520 mm above the ground was sampled by polyurethane foam disks held in down-faced cartridges. The samplers were tested at three sites: A: an extremely contaminated site, B: a site near A, and C: a background site on a university campus. Vertical concentration gradients were revealed for PAH_LMW4 within a thin layer close to soil surface at the three sites. PAH concentrations either decreased (Site A) or increased (Sites B and C) with height, suggesting either deposition to or evaporation from soils. The sampler is a useful tool for investigating air-soil exchange of gaseous phase semi-volatile organic chemicals.     

Infrared analysis for counterfeit electronic parts detection and supply chain validation

Within the electronics industry, counterfeit electronic components entering the supply chain have steadily become an increasing threat accounting for more than 8 % of global merchandise trade and an annual $600 billion enterprise. Currently, there are not many cost-effective and nonintrusive solutions for counterfeit detection of electronic parts. In this paper, the authors present a statistical approach for detecting counterfeit components based on infrared (IR) analysis by the use of independent component analysis (ICA). As a prominent higher-order statistical analysis technique, ICA is capable of extracting relevant features from IR data. The latest applications and the extended algorithms of ICA have been elucidated for the purposes of classification and identification of counterfeit electronic parts. The theoretical framework of ICA is presented along with extensive experimental results to illustrate its feature extraction function in counterfeit electronic parts detection.     

Estimating dissolved reactive phosphorus concentration in surface runoff water from major Ontario soils

Phosphorus (P) loss from agricultural land in surface runoff can contribute to eutrophication of surface water. This study was conducted to evaluate a range of environmental and agronomic soil P tests as indicators of potential soil surface runoff dissolved reactive P (DRP) losses from Ontario soils. The soil samples (0- to 20-cm depth) were collected from six soil series in Ontario, with 10 sites each to provide a wide range of soil test P (STP) values. Rainfall simulation studies were conducted following the USEPA National P Research Project protocol. The average DRP concentration (DRP30) in runoff water collected over 30 min after the start of runoff increased (p < 0.001) in either a linear or curvilinear manner with increases in levels of various STPs and estimates of degree of soil P saturation (DPS). Among the 16 measurements of STPs and DPSs assessed, DPS(M3) 2 (Mehlich-3 P/[Mehlich-3 Al + Fe]) (r2 = 0.90), DPS(M3)-3 (Mehlich-3 P/Mehlich-3 Al) (r2 = 0.89), and water-extractable P (WEP) (r2 = 0.89) had the strongest overall relationship with runoff DRP30 across all six soil series. The DPS(M3)-2 and DPS(M3)-3 were equally accurate in predicting runoff DRP30 loss. However, DPS(M3)-3 was preferred as its prediction of DRP30 was soil pH insensitive and simpler in analytical procedure, ifa DPS approach is adopted.     

Assessing biodegradation potential of PAHs in complex multi-contaminant matrices

This study sought to extend validation of a cyclodextrin based extraction method for the assessment of PAH-biodegradation potential to complex multi-contaminant matrices. To this end, four reference materials (RMs) were produced by blending, in different proportions, soils impacted with diesel, lubricating oil and spent oxide. These reference materials had modest ∑PAH (16 US EPA) concentrations that ranged from 5.6 ± 0.5 to 44.4 ± 4.5 mg kg⁻¹. However, extractable petroleum hydrocarbon (EPH) concentrations were comparatively high (up to 2520 ± 204 mg kg⁻¹). To complement these RMs, two further soils from a municipal gas plant (MGP) with highly elevated concentration of PAHs ranging from 877 ± 52 to 2620 ± 344 mg kg⁻¹ were also tested. Results showed, regardless of matrix complexity, that PAH biodegradation within the four RM substrates, and two MGP soils correlated well with biodegradation predicted by hydroxypropyl-β-cyclodextrin (HPCD) extraction.     

Development of the pericalymma larva of Solemya reidi (Bivalvia: Cryptodonta: Solemyidae) as revealed by light and electron microscopy

Solemya reidi Bernard 1980 is a gutless protobranch bivalve known to possess intracellular chemoautotrophic bacterial symbionts in its gill. A light and electron microscope study on the embryology and larval development of S. reidi provides data for the bivalve Subclass Cryptodonta. S. reidi spontaneously spawned large eggs (271 m in diameter), which developed within individual gelatious egg capsules. The first several cleavages were equal and a distinct molluscan cross was formed at the animal pole of the embryo, features previously unreported in bivalve development. Lecithotrophic pericalymma larvae (similar to the larvae of paleotaxodont protobranch bivalves and aplacophoran molluscs) hatched at 18 to 24 h and remained in the water column for a further 5 d at 10°C. At hatching, larvae measured from 360 to 440 m in length and from 225 to 265 m in cross-sectional diameter. Definitive adult structures developed within an epithelial locomotory test entirely covered with compound cilia. The test histolysed at metamorphosis and was ingested throught the mouth into the perivisceral cavity. Length and height of the shell following metamorphosis was 433 m (±42 m, n=16) and 282 m (± 29 m, n=13), respectively. Primary data and data from the literature show that the type of larval development in both paleotaxodont and cryptodont bivalves cannot be reliably estimated from egg or prodissoconch sizes.