Characterisation of the dilute HCl extraction method for the identification of metal contamination in Antarctic marine sediments

A regional survey of potential contaminants in marine or estuarine sediments is often one of the first steps in a post-disturbance environmental impact assessment. Of the many different chemical extraction or digestion procedures that have been proposed to quantify metal contamination, partial acid extractions are probably the best overall compromise between selectivity, sensitivity, precision, cost and expediency. The extent to which measured metal concentrations relate to the anthropogenic fraction that is bioavailable is contentious, but is one of the desired outcomes of an assessment or prediction of biological impact. As part of a regional survey of metal contamination associated with Australia's past waste management activities in Antarctica, we wanted to identify an acid type and extraction protocol that would allow a reasonable definition of the anthropogenic bioavailable fraction for a large number of samples. From a kinetic study of the 1 M HCl extraction of two Certified Reference Materials (MESS-2 and PACS-2) and two Antarctic marine sediments, we concluded that a 4 h extraction time allows the equilibrium dissolution of relatively labile metal contaminants, but does not favour the extraction of natural geogenic metals. In a regional survey of 88 marine samples from the Casey Station area of East Antarctica, the 4 h extraction procedure correlated best with biological data, and most clearly identified those sediments thought to be contaminated by runoff from abandoned waste disposal sites. Most importantly the 4 h extraction provided better definition of the low to moderately contaminated locations by picking up small differences in anthropogenic metal concentrations. For the purposes of inter-regional comparison, we recommend a 4 h 1 M HCl acid extraction as a standard method for assessing metal contamination in Antarctica.     

Aseptically collected calf serum as an effective alternative to fetal calf serum in the culture of amniotic fluid cells

The growth-promoting activities of three different bovine sera have been compared in primary and secondary amniotic fluid cell cultures. In secondary amniotic fluid cell micro- cultures, aseptically collected calf serum (CS) was slightly, though not significantly more effective than fetal calf serum (FCS) in promoting DNA synthesis, while newborn calf serum (NCS) was significantly less effective than either CS or FCS. All three sera were optimally effective at concentrations of 10 per cent (v/v). Significant variation in quality occurred within four batches of each of CS and FCS, but not within four batches of NCS. A selected batch of CS was significantly more effective in promoting the growth of primary amniotic fluid cell cultures than were a number of batches of FCS then in routine laboratory use. It is suggested that CS may serve as an effective and economical alternative to FCS in the culture of amniotic fluid cells, thereby expanding the scope of serum batch testing. A possible explanation for the varying growth-promoting activities of different sera is discussed.     

Evaluation of diffusive gradients in thin film (DGT) samplers for measuring contaminants in the Antarctic marine environment

This work has been the first application of DGT samplers for measuring metals in water and sediment porewater in the Antarctic environment, and whilst DGT water sampling was restricted to quantification of Cd, Fe and Ni, preconcentration using Empore chelating disks provided results for an additional nine elements (Sn, Pb, Al, Cr, Mn, Co, Cu, Zn, As). Although higher concentrations were measured for some metals (Cd, Ni, Pb) using the Empore technique, most likely due to particulate-bound or colloidal species becoming entrapped in the Empore chelating disks, heavy metal concentrations in the impacted Brown Bay were found to be comparable with the non-impacted O'Brien Bay. Sediment porewater sampling using DGT also indicated little difference between Brown Bay and O'Brien Bay for many metals (Cd, Al, Cr, Co, Ni, Cu), however, greater amounts of Pb, Mn, Fe and As were accumulated in DGT probes deployed in Brown Bay compared with O'Brien Bay, and a higher accumulation of Sn was observed in Brown Bay inner than any of the other three sites sampled. Comparison of DGT derived porewater concentrations with actual porewater concentrations showed limited resupply of Cd, Pb, Al, Cr, Mn, Co, Ni, Cu, Zn and As from the solid phase to porewater, with these metals appearing to be strongly bound to the sediment, however, resupply of Fe and Sn was apparent. Based upon our observations here, we suggest that Sn, and to a lesser extent Pb, are critical contaminants.     

Evaluation of geochemical methods for discrimination of metal contamination in Antarctic marine sediments: a case study from Casey Station

Detecting anthropogenic metal contamination in regional surveys can be particularly difficult when there is a lack of pre-disturbance data, especially when trying to differentiate low to moderate levels of contamination from background values. Furthermore, comparisons with other regional studies are confounded by differing analytical methods used and variations in sediment properties such as grainsize. Several types of geochemical technique, including weak acid partial extraction, strong acid extractions and total digestion have been used. Attempts have been made to overcome the influence that grainsize has on chemical concentrations in heterogeneous environments by analysing the fines, typically the mud fraction (<63 microm), in an attempt to improve the detection of anthropogenic contamination. Here we compare a weak acid partial extraction using 1M HCl and total digestion methods for a regional survey of reference and impacted sites in Antarctica using both whole sediment (<2 mm) and mud (<63 microm) fractions. The 1M partial extraction on whole sediment (<2 mm) most closely distinguished weakly, or moderately, impacted sites from reference locations. It also identified small scale within-location spatial variation in metal contamination that the total digest did not detect. Compared with total digests or analysis of the <63 microm fraction alone, this method minimised the possibility of a Type II statistical error in the regional survey - that is, failing to identify a site as being contaminated when it has elevated metal concentrations. To allow inter-regional comparison of sediment chemistry data from elsewhere in Antarctica, and also more generally, we recommend a 1M HCl partial extraction on whole sediment (<2 mm).     

Study of biological stabilization processes of cattle and poultry manure by thermogravimetric analysis and (13)C NMR

The biological stabilization process of cattle and poultry manure was studied using thermogravimetric analysis and (13)C nuclear magnetic resonance. The stabilization processes carried out were composting, anaerobic digestion and a mixed process (partly aerobic, partly anaerobic). It was observed from the analyzed samples that the biological stabilization processes reduce the volatile content of the bio-wastes and increase the degree of aromaticity. The stabilization of cattle manure by means of aerobic processes was able to further oxidize and enriched in aromatic compounds the bio-waste when compared with the digestion process. On the other hand, the stabilization of poultry manure resulted in a greater aromatization under the digestion process. Stabilized samples with a high degree of aromaticity presented a lower volatile content accompanied by a reduction in the intensity of the differential thermogravimetry peak registered under an inert atmosphere, indicative of the thermal decomposition of the organic matter. The thermal decomposition of all the analyzed materials (fresh and stabilized samples) commenced at around 200 degrees C but for the digested poultry manure, which decomposition initiated close to 250 degrees C. All stabilized samples yielded a lower degree of volatilization to that one observed in fresh samples.     

Pyrolysis of virgin and waste polypropylene and its mixtures with waste polyethylene and polystyrene

A comparison of waste and virgin polypropylene (PP) plastics under slow pyrolysis conditions is presented. Moreover, mixtures of waste PP with wastes of polyethylene (PE) and polystyrene (PS) were pyrolyzed under the same operating conditions. Not only the impact of waste on degradation products but also impacts of the variations in the mixing ratio were investigated. The thermogravimetric weight loss curves and their derivatives of virgin and waste PP showed differences due to the impurities which are dirt and food residues. The liquid yield distribution concerning the aliphatic, mono-aromatic and poly-aromatic compounds varies as the ratio of PP waste increases in the waste plastic mixtures. In addition to this, the alkene/alkane ratio of gas products shows variations depending on the mixing ratio of wastes.     

Recyling of plastic wastes via pyrolysis

Pyrolysis for the simultaneous generation of oils and gases can be convenient to obtain hydrocarbons and even to recover crude petrochemicals or to generate energy from waste plastics. A Gray–King apparatus has been used to pyrolyze waste polyethylene (PE), polystyrene (PS), both separately and with different compositions. Thermogravimetric analysis of waste plastics indicated the critical temperatures, which should be effective for pyrolysis. The chosen heating rate was low in order to achieve higher liquid yields. The results showed that waste PS yielded higher liquid, and waste PE yielded higher gaseous products. The dominant liquid product of PS waste was styrene whereas for waste PE, prophenylbenzene was the dominant pyrolysis product.     

Investigation of evaporation and biodegradation of fuel spills in Antarctica: II-extent of natural attenuation at Casey Station

In many temperate regions, fuel and oil spills are sometimes managed simply by allowing natural degradation to occur, while monitoring soils and groundwater to ensure that there is no off-site migration or on-site impact. To critically assess whether this approach is suitable for coastal Antarctic sites, we investigated the extent of evaporation and biodegradation at three old fuel spills at Casey Station. Where the contaminants migrated across frozen ground, probably beneath snow, approximately half the fuel evaporated in the first few months prior to infiltration at the beginning of summer. Once in the ground, however, evaporation rates were negligible. In contrast, minor spills from fuel drums buried in an abandoned waste disposal site did not evaporate to the same extent. Biodegradation within all three spill sites is generally very minor. We conclude that natural attenuation is not a suitable management strategy for fuel-contaminated soils in Antarctic coastal regions.     

Processes of distribution of pharmaceuticals in surface freshwaters: implications for risk assessment

The global consumption and production of pharmaceuticals is increasing concomitantly with concern regarding their environmental fate and effects. Active pharmaceutical ingredients are mainly released into the aquatic environment through wastewater effluent discharge. Once in the environment, pharmaceuticals can undergo processes of natural attenuation, i.e. dilution, sorption, transformation, depending on physico-chemical properties of the compound, such as water solubility, lipophilicity, vapour pressure, and environmental conditions, such as pH, temperature and ionic strength. A major natural attenuation process is the sorption on dissolved organic matter, colloids, suspended solids and sediments, which in turn control pharmaceuticals distribution, residence time and persistence in aquatic systems. Here we review studies of sorption capacity of natural sorbents to pharmaceuticals. These report on the importance of several environmental and sorbent-specific properties, such as the composition, quality, and amount of the sorbent, and the environmental pH, which determines the speciation of both the sorbent and compound. The importance of accounting for distribution processes on freshwater sorbents for any determination of environmental concentrations of pharmaceuticals is apparent, while the reliability of surrogate standards for measuring dissolved organic matter (DOM) distribution is evaluated in the context of the need for robust environmental risk assessment protocols.