Polybrominated diphenyl ethers and polybrominated biphenyls in Australian sewage sludge

This paper presents a brief review of the international scientific literature of polybrominated diphenyl ethers (PBDEs) and polybrominated biphenyls (PBBs) in sewage sludge and a survey of these compounds in sewage sludge from 16 Australian wastewater treatment plants (WWTPs). The SigmaPBDE mean concentration in the Australian study was 1137microgkg(-1) dry weight (d.w.) (s.d. 1116) and ranged between 5 and 4 230microgkg(-1)d.w. The urban mean of 1308microgkg(-1) (s.d. 1320) and the rural mean of 911microgkg(-1) (s.d. 831) are not statistically different and are similar to levels in European sludges. Principal components analysis was performed on the data set and revealed that 76% of the data variation could be explained by two components that corresponded to overall concentration of the pentaBDE and the decaBDE commercial formulations. An analysis of variance was performed comparing PBDEs levels at three WWTPs over the years 2005 and 2006, finding differences between treatment plants (BDE-47) but no significant difference in PBDE levels in the years 2005 and 2006. Low levels of BB-153 were detected in all samples of this survey (n=16); mean 0.6microgkg(-1)d.w. (s.d. 0.5). This compound has rarely been reported in any other study of sewage sludges undertaken outside Australia. This work highlights the need for a risk assessment of PBDEs in sewage sludge when used for land application, taking into account typical levels found in Australian sludges and soils.     

The mobility of thiobencarb and fipronil in two flooded rice-growing soils

The mobility of the rice pesticides thiobencarb (S-[(4-chlorophenyl) methyl] diethylcarbamothioate) and fipronil ([5-amino-3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]pyrazole) were investigated in the glasshouse under flooded conditions using two Australian rice-growing soils. When using leakage rates of 10 mm day(-1), less than 20% of applied thiobencarb and fipronil remained in the water column after 10 days due to rapid transfer to the soil phase. Up to 70% and 65% of the applied thiobencarb and fipronil, respectively, were recovered from the 0-1 cm layer of soils. Only 5-7% of each pesticide was recovered from the 1-2 cm layer, and less than 2% was recovered from each 1 cm layer in the 2-10 cm region of the soils. Analysis of the water leaking from the base of the soil cores showed between 5-10% of the applied thiobencarb and between 10-20% of the applied fipronil leaching from the soil cores. The high levels of pesticide in the effluent was attributed to preferential flow of pesticide-laden water via soil macropores resulting from the wetting and drying process, worm holes and root channels.     

Direct measurement of fugitive emissions of hydrocarbons from a refinery

Refineries are a source of emissions of volatile hydrocarbons that contribute to the formation of smog and ozone. Fugitive emissions of hydrocarbons are difficult to measure and quantify. Currently these emissions are estimated based on standard emission factors for the type and use of equipment installed. Differential absorption light detection and ranging (DIAL) can remotely measure concentration profiles of hydrocarbons in the atmosphere up to several hundred meters from the instrument. When combined with wind speed and direction, downwind vertical DIAL scans can be used to calculate mass fluxes of the measured gas leaving the site. Using a mobile DIAL unit, a survey was completed at a Canadian refinery to quantify fugitive emissions of methane, C2+ hydrocarbons, and benzene and to apportion the hydrocarbon emissions to the various areas of the refinery. Refinery fugitive emissions as measured with DIAL during this demonstration study were 1240 kg/hr of C2+ hydrocarbons, 300 kg/hr of methane, and 5 kg/hr of benzene. Storage tanks accounted for over 50% of the total emissions of C2+ hydrocarbons and benzene. The coker area and cooling towers were also significant sources. The C2+ hydrocarbons emissions measured during the demonstration amounted to 0.17% of the mass of the refinery hydrocarbon throughput for that period. If the same loss were repeated throughout the year, the lost product would represent a value of US$3.1 million/yr (assuming US$40/bbl). The DIAL-measured hourly emissions of C2+ hydrocarbons were 15 times higher than the emission factor estimates and gave a different perspective on which areas of the refinery were the main source of emissions. Methods, such as DIAL, that can directly measure fugitive emissions would improve the effectiveness of efforts to reduce emissions, quantify the reduction in emissions, and improve the accuracy of emissions data that are reported to regulators and the public.     

Carbon, nitrogen balances and greenhouse gas emission during cattle feedlot manure composting

Carbon and N losses reduce the agronomic value of compost and contribute to greenhouse gas (GHG) emissions. This study investigated GHG emissions during composting of straw-bedded manure (SBM) and wood chip-bedded manure (WBM). For SBM, dry matter (DM) loss was 301 kg Mg(-1), total carbon (TC) loss was 174 kg Mg(-1), and total nitrogen (TN) loss was 8.3 kg Mg(-1). These correspond to 30.1% of initial DM, 52.8% of initial TC, and 41.6% of initial TN. For WBM, DM loss was 268 kg Mg(-1), TC loss was 154 kg Mg(-1), and TN loss was 1.40 kg Mg(-1), corresponding to 26.5, 34.5, and 11.8% of initial amounts. Most C was lost as CO2 with CH4 accounting for <6%. However, the net contribution to greenhouse gas emissions was greater for CH4 since it is 21 times more effective at trapping heat than CO2. Nitrous oxide (N2O) emissions were 0.077 kg N Mg(-1) for SBM and 0.084 kg N Mg(-1) for WBM, accounting for 1 to 6% of total N loss. Total GHG emissions as CO2-C equivalent were not significantly different between SBM (368.4 +/- 18.5 kg Mg(-1)) and WBM (349.2 +/- 24.3 kg Mg(-1)). However, emission of 368.4 kg C Mg(-1) (CO2-C equivalent) was greater than the initial TC content (330.5 kg Mg(-1)) of SBM, raising the question of the net benefits of composting on C sequestration. Further study is needed to evaluate the impact of composting on overall GHG emissions and C sequestration and to fully investigate livestock manure management options.     

Study of individual reactions of the sour compression process for the purification of oxyfuel-derived CO2

Following the feasibility study of sour compression process as a novel purification method of producing NO_x-free, SO₂-free oxyfuel-derived CO₂ using actual fluegas, in this paper, we present the study of the individual reactions taking place in the process in a controlled environment. We have previously showed that an increase of NO/NO₂ concentration in the inlet stream is beneficial for SO₂ removal as NO₂ promotes SO₂ oxidation and the further removal as liquid acid. In this study we show that the reaction SO₂ + NO₂ → SO₃ + NO does not take place significantly in the absence of liquid water at a range of conditions relevant to the sour compression process. When liquid water is present, SO₂ is oxidised by NO₂ regenerating NO with the rate of conversion of SO₂ being dependent on the acid concentration in the liquid. The formation of small liquid droplets where very low levels of pH (?0) can be reached is shown to be of great importance to the SO₂ + NO₂ conversion process.     

Complex mixtures that may contain mutagenic and/or genotoxic components: a need to assess in vivo target-site effect(s) associated with in vitro-positive(s)

A battery of short-term in vitro assays and/or in vivo protocols to evaluate single-agent mutagenicity and/or genotoxicity is available. However, a protocol to assess the effect(s) of complex mixtures in vivo following a positive test finding in vitro remains difficult. Complex interactions may occur in vivo because component pharmacokinetics increases the unpredictability of pharmacodynamic outcomes. The question arises as to whether in vitro mutagenic component(s) of a complex mixture, probably unidentified, reach target organ(s) in vivo at a sufficient concentration. To address the issue of an in vitro positive, standard in vivo chromosome damage assays to test both mixtures and fractions could be conducted but, to assess site-of-contact effects, the alkaline single cell-gel electrophoresis ("comet") assay or DNA reactivity (e.g., (32)P-postlabelling of DNA adducts) might be employed. A newer approach may be the derivation of a "biochemical-cell fingerprint" of potential target sites using infrared microspectroscopy. There is interest in platforms such as gene expression, proteomics, epigenomics or metabolomics as biomarkers of signature genotoxic or non-genotoxic mechanisms. One still needs to address whether a mutagenic and/or genotoxic component reaches a target organ. An approach to track levels of target-organ exposure may be to radio-label components with a short-lived positron-emitting radionuclide. The parent compound retains its physicochemical properties whilst allowing non-invasive in vivo tissue-specific imaging. However, determining target-organ concentration(s) and effect(s) in vivo remains a difficult challenge.     

Redox reactions in the Fe-As-O2 system

We have examined two redox reactions involving arsenic and iron at near-neutral pH: the reduction of As(V) by Fe(II) under anoxic conditions, and the co-oxidation of As(III) during Fe(II) oxygenation. We also considered the impact of goethite, pH buffers, and radical scavengers on these reactions. In a series of anoxic experiments, Fe(II) was found to reduce As(V) in the presence of goethite, but not in homogeneous solution. The reaction rate increased with increasing pH and Fe(II) concentration, but in all cases was relatively slow. In aerobic experiments, the kinetics of Fe(II) oxygenation at neutral pH, and the corresponding oxidation of As(III) were found to depend heavily on pH buffer type and concentration. The classic formulation of Fe(II) oxidation by oxygen, involving four single-electron transfers, was reviewed and found to be inadequate for explaining observed oxidation of Fe(II) and As(III). Widely cited rate constants for Fe(II) oxygenation originate from experiments conducted in carbonate buffer, and do not match observations made in phosphate, MES, or HEPES systems. In phosphate buffer, Fe(II) oxidation is rapid and dependent on phosphate concentration. In MES and HEPES buffers, Fe(II) oxidation is much slower due to the lack of labile ferrous iron species. Oxygenation of Fe(II) appears to proceed through different mechanisms in phosphate and MES or HEPES systems. In both cases, reactive intermediary species are produced which can oxidize As(III). These oxidants are not the hydroxyl radical, but may be Fe(IV) species.     

Type 'A' and 'B' recovery revisited: the role of field-edge habitats for Collembola and macroarthropod community recovery after insecticide treatment

Previous work has identified two patterns of arthropod recovery after insecticide applications to arable crops: dispersal-mediated recolonisation from untreated areas (Type A) and recolonisation within treated areas assisted by reduced predation (Type B). In this study, connectivity between field-edge habitats was manipulated using barriers to investigate whether a crop edge and adjacent hedgerow influence recolonisation of an insecticide-treated crop by surface-active Collembola and other arthropods. Collembola recovery patterns differed among closely-related taxa. Epigeic collembolan and macroarthropod communities were more diverse and abundant, and rates of artificial prey predation were higher, in sprayed crop areas connected to both hedgerow and unsprayed crop edge than in sprayed areas connected to the unsprayed edge alone. These findings indicate that effectiveness of unsprayed crop edges as sources of field recolonisation may depend on adjoining field margin habitats. An assumption in risk assessment that unsprayed crop edges assist population recovery within treated areas is not supported.     

Accumulation of Endosulfan in Wild Rat, Rattus norvegious as a Result of Application to Soya Bean in Mazoe (Zimbabwe)

An assessment of levels of endosulfan and endosulfan sulphate in rats collected from a plot sprayed with endosulfan was carried out for a period of four months. The analysis was carried out in the livers, muscles and fatty tissues of the rats using Gas Chromatography. Samples were ground with sodium sulphate and aluminium oxide and the analyte soxhlet extracted with hexane. The extract was then cleaned by florisil column chromatography. Levels of endosulfan in rats were found to range in livers from 0.356 to 5.807 ppb, in muscles from 0.089 to 5.167 ppb and in fatty tissues from 0.083 to 4.785 ppb. Levels of endosulfan sulphate correlated well with those of endosulfan and ranged in livers from 0.00 to 3.96 ppb, in muscles from 0.00 to 3.37 ppb and in fatty tissue from 0.00 to 2.93 ppb. In the control rats samples, collected from an unsprayed area in the city of Harare (University of Zimbabwe), no endosulfan could be detected.