Monobromo and higher brominated congeners of the marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1)

The marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) is widely distributed in the environment. In this study, we screened samples which have previously been found to contain remarkably high residues of Q1 (blubber of marine mammals from Australia, samples from Antarctica, human milk from the Faroe Island) for the additional presence of mixed chlorinated and brominated congeners. Using GC/ECNI-MS, all samples tested were positive and many contained four out of five possible bromohexachloro congeners (BrCl6-MBPs), five out of 14 possible dibromopentachloro congeners (Br2Cl5-MBPs), five of 21 possible tribromotetrachloro-congeners (Br3Cl4-MBPs), as well as several higher brominated congeners. About 20 heptahalo congeners of Q1 are described for the first time in the scientific literature. Isomers eluted within about one minute, respectively. Hence it is possible, that the peak clusters identified may be composed of more, co-eluting congeners. Similarities in the GC/ECNI-MS mass spectra with polychlorinated biphenyls (PCBs) were addressed. We also suggest an acronym system similar to that in use for polychlorinated biphenyls that may simplify the use of this substance class in scientific papers. In the samples from Australia, BrCl6-MBPs and Br2Cl5-MBPs amounted for 7-27.5% and 0.4-4.2% of Q1, respectively whereas Br3Cl4-MBPs and higher brominated MBPs were found in the range of <1% of Q1 or less.     

Plasma concentration of organochlorine compounds is associated with age and not obesity

It has been suggested that obese individuals, because of an increased dilution space (body fat) for lipophilic organochlorines compounds, may have greater levels of toxic pollutants than lean sedentary individuals. It is important to further examine this possibility because of the potential contribution of organochlorine pesticides in the development of Parkinson's disease and other neurological diseases. The aim of this study was to further investigate the relationship between the magnitude of obesity and the plasma concentration of organochlorines for a wide range of BMI (with participants at steady state body weight). Fifty-three individuals were selected on the basis of their body mass index (BMI): lean controls (n=16; mean BMI 22.8+/-2.2 kg/m(2); mean age 38.8+/-9.4 years), obese individuals (n=19; mean BMI 33.4+/-3.0 kg/m(2); mean age 38.6+/-7.6 years) and morbidly obese individuals (n=18; mean BMI 49.3+/-6.5 kg/m(2); mean age 44.3+/-9.2 years). Blood samples were analyzed for organochlorine compounds. The relationship between the total plasma organochlorine concentration and BMI was tested using a multiple regression analysis. Age was included in the model. There was no relationship between the total plasma organochlorine concentration and BMI. Organochlorine concentrations, however, were correlated with age (BMI-adjusted R(2)=0.46; p<0.001). At steady state body weight, toxic pollutant concentrations are not associated to obesity but strongly correlate with age.     

Accumulation and partitioning of heavy metals in mangroves: a synthesis of field-based studies

We report the findings of a comparative analysis examining patterns of accumulation and partitioning of the heavy metals copper (Cu), lead (Pb) and zinc (Zn) in mangroves from available field-based studies to date, employing both species level analyses and a phylogenetic approach. Despite mangroves being a taxonomically diverse group, metal accumulation and partitioning for all metals examined were broadly similar across genera and families. Patterns of metal accumulation were also similar regardless of whether species were classified as salt secreting or non-secreting. Metals were accumulated in roots to concentrations similar to those of adjacent sediments with root bio-concentration factors (BCF; ratio of root metal to sediment metal concentration) of 1< or =. Root BCFs were constant across the exposure range for all metals. Metal concentrations in leaves were half that of roots or lower. Essential metals (Cu and Zn; translocation factors (TF; ratio of leaf metal to root metal concentration) of 0.52 and 0.53, and leaf BCFs of 0.47 and 0.51, respectively) showed greater mobility than non-essential metals (Pb; TF of 0.31 and leaf BCF of 0.11). Leaf BCFs for the essential metals Cu and Zn decreased as environmental concentrations increased. The non-essential metal Pb was excluded from leaf tissue regardless of environmental concentrations. Thus mangroves as a group tend to operate as excluder species for non-essential metals and regulators of essential metals. For phytoremediation initiatives, mangrove ecosystems are perhaps best employed as phytostabilisers, potentially aiding in the retention of toxic metals and thereby reducing transport to adjacent estuarine and marine systems.     

Carbon/nitrogen ratio as a major factor for predicting the effects of organic wastes on soil bacterial communities assessed by DNA-based molecular techniques

Background, aim, and scope  

Current Australian legislation permits the beneficial application of grease trap waste (GTW) to agricultural soil, viewing it as a beneficial source of organic matter and soil conditioner containing no/low amounts of metals or pathogenic organisms. However, little is known about the influence of GTW on soil bacterial community. A field experiment was established at Menangle in south western Sydney in Australia to quantitatively assess the impacts of different types (GTW CO and GTW CL) and amounts of GTW application on the soil bacterial community and diversity. Furthermore, a municipal solid waste (MSW) compost was simultaneously examined to compare against the other organic wastes. Knowledge about the shifts in microbial community structure and diversity following the applications of organic wastes could help to evaluate the ecological consequences on the soil and thus to develop sound regulatory guidelines for the beneficial reuse of organic wastes in agricultural lands.     

Theoretical versus observed gas-particle partitioning of carbonyl emissions from motor vehicles

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120-580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

The seasonal cycles and photochemistry of C2–C5 alkanes at Mace Head

Continuous in-situ measurements of NMHCs at Mace Head, Ireland during two full annual cycles from January 2005 to January 2007 were used to investigate NMHC emission sources and transport including dilution and photochemical oxidation. The Mace Head research station is ideally located to sample a wide range of air masses including polluted European transport, clean North Atlantic and Arctic air masses and the ultra-clean, Southern Atlantic air masses. The variety in air mass sampling is used to investigate interaction of emissions, transport, dilution and photochemistry. Variability of long-lived hydrocarbon ratios is used to assess and estimate typical transport times from emission source to the Mace Head receptor. Seasonality in the ratios of isomeric alkane pairs (for butane and pentanes) are used to assess the effects of atmospheric transport and photochemical ageing. Finally, the natural logarithms of NMHC ratios are used to assess photochemical oxidation.     

Bird conservation and the land sharing-sparing continuum in farmland-dominated landscapes of lowland England

Empirical evidence from many regions suggests that most species would be least negatively affected if human food demand were met through high-yield agricultural production and conservation of nonfarm ecosystems (land sparing), rather than through wildlife-friendly farming over a larger area (land sharing). However, repeated glaciation and a long history of agriculture may lead to different results in regions such as western Europe. We compared the consequences of land sparing and land sharing on breeding bird species in 2 lowland regions of England, The Fens, with 101 species, and Salisbury Plain, with 83. We derived density–yield responses for each species and then estimated regional population size under regional food production strategies, including land sharing and land sparing, a range of intermediate strategies, and a novel mixed strategy. In both regions, more species achieved maximum regional population size under land sparing than land sharing. In The Fens, the majority of birds were loser species (estimated to have smaller populations under all food production strategies than in the preagricultural baseline scenario), whereas in Salisbury Plain the majority were winners (smaller populations in the preagricultural baseline scenario). Loser species overwhelmingly achieved maximum regional population size under land sparing, whereas winner species achieved maximum regional population size under either land sharing or an intermediate strategy, highlighting the importance of defining which groups of species are the target of conservation. A novel 3-compartment strategy (combining high-yield farming, natural habitat, and low-yield farming) often performed better than either land sharing or land sparing. Our results support intermediate or 3-compartment land-sparing strategies to maximize bird populations across lowland agricultural landscapes. To deliver conservation outcomes, any shift toward land sparing must, however, ensure yield increases are sustainable in the long term, do not entail increased negative effects on surrounding areas, and are linked to allocation of land for nature.     

Benzo[b]fluoranthene,a Potential Alternative to Benzo[a]pyrene as an Indicator of Exposure to Airborne PAHs in the Vicinity of Söderberg Aluminum Smelters

ABSTRACT

Benzo[b]fluoranthene (B[b]F) was used in relative abundance ratios (RARs), a parameter obtained by dividing the concentration of individual polycyclic aromatic hydrocarbons (PAHs) found in a given sample by the concentration of B[b]F in the same sample. The B[b]F RARs were derived for PAH concentrations measured at stacks and sampling stations in the vicinity of two Söderberg aluminum horizontal stud smelters (HSSs). The samples collected were analyzed by high-performance liquid chromatography using UV and fluorescence detection. A total of 15 PAHs were analyzed, but, due to the inefficiency of the sampling method used in collecting gaseous PAHs, only particulate PAHs were considered. Comparisons between the B[b]F RARs obtained simultaneously at the source (stack) and those obtained at sampling stations at the two smelters showed that B[b]F degrades more slowly than or at the same rate as most other particulate PAHs monitored. Twenty-three months of urban sampling in the vicinity of one of the aluminum HSSs are also presented, and the results indicate that B[b]F is more stable than all other particulate PAHs investigated. Sampling conducted during a smelter shutdown period confirmed that B[b]F was a much better marker of this source than was benzo[a]pyrene (B[a]P), the usual indicator. The remarkable stability of the benzo[k]fluoranthene (B[k]F)/B[b]F ratio is also discussed.     

Effects of synthetic pyrethroids and methidation on activities of some digestive enzymes in carp (Cyprinus carpio L.)

Abstract

The effects of pyrethroid pesticides (deltamethrin, permethrin and cypermethrin) and an organophosphate ester (methidation) on the activities of carp trypsin, α‐chymotrypsin, carboxypeptidase A and lipase were studied. The enzymes were isolated from the gastrointestinal tract and the effects of the pesticides were investigated during incubation for 5 min. The activity of trypsin was influenced only slightly by the presence of deltamethrin and methidation, whereas permethrin and cypermethrin caused significant inhibition. The pyrethroid pesticides at lower concentrations resulted in a slight activation of α‐chymotrypsin. Methidation inhibited the α‐chymotrypsin activity by about 20%. These pesticides modified the lipase activity to a lesser extent; the highest inhibition was measured with cypermethrin. The carboxypeptidase A activity was inhibited by both pyrethroid pesticides and methidation. The results suggest that these pesticides might interact with the active conformation of the studied hydrolytic enzymes, resulting in changes in their activities.     

Feedbacks between bivalve density, flow, and suspended sediment concentration on patch stable states

We explore the role of biophysical feedbacks occurring at the patch scale (spatial scale of tens of meters) that influence bivalve physiological condition and affect patch stability by developing a numerical model for the pinnid bivalve, Atrina zelandica, in cohesive sediments. Simulated feedbacks involve bivalve density, flow conditions (assumed to be primarily influenced by local water depth and peak current speed), suspended sediment concentration (evaluated through a balance between background concentration, deposition, and erosion), and changes in the physiology of Atrina derived from empirical study. The model demonstrates that high bivalve density can lead to skimming flow and to a concomitant decrease in resuspension that will affect suspended sediment concentration over the patch directly feeding back on bivalve physiology. Consequently, for a given flow and background suspended sediment load, the stability of a patch directly depends on the size and density of bivalves in the patch. Although under a range of conditions patch stability is ensured independently of bivalve density, simulations clearly indicate that sudden changes in bivalve density or suspended sediment concentration can substantially affect patch structure and lead to different stable states. The model highlights the role of interactions between organisms, flow, and broader scale environmental conditions in providing a mechanistic explanation for the patchy occurrence of benthic suspension feeders.