Sources,distribution, and acidity of sulfate–ammonium aerosol in the Arctic in winter–spring

We use GEOS-Chem chemical transport model simulations of sulfate–ammonium aerosol data from the NASA ARCTAS and NOAA ARCPAC aircraft campaigns in the North American Arctic in April 2008, together with longer-term data from surface sites, to better understand aerosol sources in the Arctic in winter–spring and the implications for aerosol acidity. Arctic pollution is dominated by transport from mid-latitudes, and we test the relevant ammonia and sulfur dioxide emission inventories in the model by comparison with wet deposition flux data over the source continents. We find that a complicated mix of natural and anthropogenic sources with different vertical signatures is responsible for sulfate concentrations in the Arctic. East Asian pollution influence is weak in winter but becomes important in spring through transport in the free troposphere. European influence is important at all altitudes but never dominant. West Asia (non-Arctic Russia and Kazakhstan) is the largest contributor to Arctic sulfate in surface air in winter, reflecting a southward extension of the Arctic front over that region. Ammonium in Arctic spring mostly originates from anthropogenic sources in East Asia and Europe, with added contribution from boreal fires, resulting in a more neutralized aerosol in the free troposphere than at the surface. The ARCTAS and ARCPAC data indicate a median aerosol neutralization fraction [NH₄⁺]/(2[SO₄^2?] + [NO₃^?]) of 0.5 mol mol^?1 below 2 km and 0.7 mol mol^?1 above. We find that East Asian and European aerosol transported to the Arctic is mostly neutralized, whereas West Asian and North American aerosol is highly acidic. Growth of sulfur emissions in West Asia may be responsible for the observed increase in aerosol acidity at Barrow over the past decade. As global sulfur emissions decline over the next decades, increasing aerosol neutralization in the Arctic is expected, potentially accelerating Arctic warming through indirect radiative forcing and feedbacks.     

Comparison of stack measurement data from R&D facilities to regulatory criteria: A case study from PNNL

Chemical emissions from research and development (R&D) activities are difficult to estimate because of the large number of chemicals used and the potential for continual changes in processes. In this case study, stack measurements taken from R&D facilities at Pacific Northwest National Laboratory (PNNL) were examined, including extreme worst-case emissions estimates and alternate analyses using a Monte Carlo method that takes into account the full distribution of sampling results. The objective of this study was to develop techniques to estimate emissions from stack measurement data that take into account a high degree of variability in the actual emissions. The results from these analyses were then compared to emissions estimated from chemical inventories. Results showed that downwind ambient air concentrations calculated from the stack measurement data were below acceptable source impact levels (ASILs) for almost all compounds, even under extreme worst-case analyses. However, for compounds with averaging periods of a year, the unrealistic but simplifying extreme worst-case analysis often resulted in calculated emissions that were above the lower level regulatory criteria used to determine modeling requirements or to define trivial releases. Compounds with 24-hr averaging periods were nearly all several orders of magnitude below all, including the trivial release, criteria. The alternate analysis supplied a more realistic basis of comparison and an ability to explore effects under different operational modes.

Implications:

Air emissions from research operations are difficult to estimate because of the changing nature of research processes and the small quantity and wide variety of chemicals used. Stack measurements can be used to verify compliance with applicable regulatory criteria. This study shows that while extreme worst-case assumptions can be used for a relatively simple initial comparison, methods that take into account the full range of measurement data are needed to provide a more realistic estimate of emissions for comparison to regulatory criteria, particularly those criteria that define trivial levels of environmental concern.     

Trends of PCDD/F and PCB concentrations and depositions in ambient air in Northwestern Germany

Time series of polychlorinated dioxins and furans (PCDD/F) and polychlorinated biphenyls (PCB) in ambient air of a large conurbation in North-Western Germany are presented and analyzed. The trend of PCDD/F concentrations, starting from as early as 1988, shows a pronounced decrease by at least one order of magnitude, demonstrating that the emission reductions were effective. The PCDD/F depositions also have decreased by a factor of 5 since 1992. However, both trends have leveled out since 2005. Time series of PCB concentrations and depositions starting in 1994 show only slight decreases for the concentrations and almost no decrease for the depositions. From the decay rates following first order kinetics, half-lives in the order of 5-15 years for the PCDD/F and 15-31 years for the sum of the six indicator PCB could be calculated, which are much longer than the half-lives estimated from their reactivity towards the OH radical. Apparently, small fresh emissions (PCDD/F), considerable secondary emissions and evaporation from contaminated soils slow down their decay in the atmosphere of big conurbations. Analyzing the decay rates of individual PCB congeners shows that the lower chlorinated and more volatile ones are removed faster than the higher chlorinated congeners, probably via gas phase reactions with the OH radical. It can be concluded from the present study that the input of PCDD/F and PCB into the food chain via the air path will continue for another one or two decades in big conurbations.     

Persistence of culturable Escherichia coli fecal contaminants in dairy alpine grassland soils

Our knowledge of Escherichia coli (E. coli) ecology in the field is very limited in the case of dairy alpine grassland soils. Here, our objective was to monitor field survival of E. coli in cow pats and underlying soils in four different alpine pasture units, and to determine whether the soil could constitute an environmental reservoir. E. coli was enumerated by MPN using a selective medium. E. coli survived well in cow pats (10(7) to 10(8) cells g(-1) dry pat), but cow pats disappeared within about 2 mo. In each pasture unit, constant levels of E. coli (10(3) to 10(4) cells g(-1) dry soil) were recovered from all topsoil (0-5 cm) samples regardless of the sampling date, that is, under the snow cover, immediately after snow melting, or during the pasture season (during and after the decomposition of pats). In deeper soil layers below the root zone (5-25 cm), E. coli persistence varied according to soil type, with higher numbers recovered in poorly-drained soils (10(3) to 10(4) cells g(-1) dry soil) than in well-drained soils (< 10(2) cells g(-1) dry soil). A preliminary analysis of 38 partial uidA sequences of E. coli from pat and soils highlighted a cluster containing sequences only found in this work. Overall, this study raises the possibility that fecal E. coli could have formed a naturalized (sub)population, which is now part of the indigenous soil community of alpine pasture grasslands, the soil thus representing an environmental reservoir of E. coli.     

Brominated flame retardants and organochlorine pollutants in eggs of little owls (Athene noctua) from Belgium

Residues of brominated diphenylethers (PBDEs), organochlorinated pesticides (OCPs) and polychlorinated biphenyls (PCBs) were measured in 40 eggs of little owls (Athene noctua), a terrestrial top predator from Belgium. The major organohalogens detected were PCBs (median 2,600 ng/g lipid, range 790-23 000 ng/g lipid). PCB 153,138/163, 170, 180 and 187 were the predominant congeners and constituted 71% of total sum PCBs. PBDEs were measurable in all samples, but their concentrations were much lower than for PCBs, with a range from 29-572 ng/g lipid (median 108 ng/g lipid). The most prevalent PBDE congeners in little owl egg samples were BDE 47, 99 and 153. This profile differs from the profile in marine bird species, for which BDE 47 was the dominant congener, indicating that terrestrial birds may be more exposed to higher brominated BDE congeners than marine birds. The fully brominated BDE 209 could be detected in one egg sample (17 ng/g lipid), suggesting that higher brominated BDEs may accumulate in terrestrial food chains. Brominated biphenyl (BB) 153 was determined in all egg samples, with levels ranging from 0.6 to 5.6 ng/g lipid (median 1.3 ng/g lipid). Additionally, hexabromocyclododecane (HBCD) could be identified and quantified in only two eggs at levels of 20 and 50 ng/g lipid. OCPs were present at low concentrations, suggesting a rather low contamination of the sampled environment with OCPs (median concentrations of sum DDTs: 826 ng/g lipid, sum chlordanes: 1,016 ng/g lipid, sum HCHs: 273 ng/g lipid). Hexachlorobenzene (HCB) and octachlorostyrene (OCS) were also found at low median levels of 134 and 3.4 ng/g lipid, respectively. Concentrations of most analytes were significantly higher in eggs collected from deserted nests in comparison to addled (unhatched) eggs, while eggshell thickness did not differ between deserted and addled eggs. No significant correlations were found between eggshell thickness and the analysed organohalogens.     

Effects of heavy metal exposure on the condition and health of nestlings of the great tit (Parus major), a small songbird species

In this study we examined the possible effects of heavy metal exposure on the condition and health of great tit nestlings (Parus major) at four study sites along a pollution gradient near a large non-ferrous smelter in Belgium during three consecutive breeding seasons. Our results showed that nestlings were indeed exposed to large amounts of heavy metals. Excrements contained significantly higher concentrations of several heavy metals (silver, arsenic, cadmium, mercury, lead) near the pollution source than at study sites farther away. When taking into account the number of young in the nest at the time of sampling, nestling body mass and condition were significantly reduced at the most polluted site. Nestlings at the two most polluted sites fledged significantly later than at the least polluted site. We also observed growth abnormalities of the legs near the pollution source. Tarsus length, wing length and haematocrit values did not differ significantly among study sites.     

Catalytic NO(chi) reduction with simultaneous dioxin and furan oxidation

The engineering, construction, performance and running costs of a catalytic flue gas cleaning component in the low dust area of a municipal waste incinerator is discussed. For this purpose, the case study of a Flemish incineration plant is presented, covering the history, the design procedure of the catalyst, relevant process data and the financial aspects. A reliable PCDD/F-destruction by means of oxidation by the catalyst to typical values of 0.001 ng TEQ/Nm3 has been demonstrated. At the same time, NO(chi)- and CO-emissions are reduced by 90% and 20% to about 50 mg/N m3 andbelow 10 mg/N m3, respectively.     

Evaluation of biochemical effects related to perfluorooctane sulfonic acid exposure in organohalogen-contaminated great tit (Parus major) and blue tit (Parus caeruleus) nestlings

A perfluorooctane sulfonic acid (PFOS) biomonitoring survey was conducted on great tit (Parus major) and blue tit (Parus caeruleus) nestlings from Blokkersdijk, a bird reserve in the proximity of a fluorochemical plant in Antwerp (Belgium) and Fort IV, a control area. PFOS, together with 11 organochlorine pesticides, 20 polychlorinated biphenyl congeners and 7 polybrominated diphenyl ethers were measured in liver tissue. The hepatic PFOS concentrations at Blokkersdijk (86–2788 and 317–3322 ng/g wet weight (ww) for great and blue tit, respectively) were among the highest ever measured and were significantly higher than at the control area (17–206 and 69–514 ng/g ww for great and blue tit, respectively). The hepatic PFOS concentration was species- and sex-independent and correlated significantly and positively with the serum alanine aminotransferase activity and negatively with the serum cholesterol and triglyceride levels in both species but did not correlate with condition or serum protein concentration. In the great tit, a significant positive correlation was observed between the liver PFOS concentration and the relative liver weight. In the blue tit, the hepatic PFOS concentration correlated positively and significantly with hematocrite values. None of the investigated organohalogen pollutants except for PFOS were suggested to be involved in the observed biological alterations.     

Eggshell strength of an obligate brood parasite: a test of the puncture resistance hypothesis

Eggs of several brood parasites have thicker and stronger shells than expected for their size. The present study evaluated the puncture resistance hypothesis for the occurrence of thick-shelled eggs in common cuckoos Cuculus canorus by investigating costs of cuckoo egg ejection in four Acrocephalus warblers—the great reed warbler A. arundinaceus, reed warbler A. scirpaceus, marsh warbler A. palustris and sedge warbler A. schoenobaenus. The three latter species all suffered ejection costs, while ejection was not costly in the larger great reed warbler. The occurrence of ejection costs was negatively related to host bill size. In the marsh warbler, we compared ejection costs in naturally parasitized nests and two experimental treatments, in which broods were parasitized artificially with great reed warbler and conspecific eggs. Hosts damaged their own eggs significantly more often when ejecting the thick-shelled cuckoo eggs than when ejecting the similarly sized but thinner-shelled great reed warbler eggs, providing some support for the puncture resistance hypothesis. Ejection of conspecific eggs did not involve any costs. Furthermore, contrary to predictions derived from the laying damage hypothesis, there was no evidence that egg damage was associated with cuckoo egg laying. Hosts damaging their own eggs during ejection were more likely to subsequently desert their clutches than those that did not. The frequency of clutches smeared with the contents of the ejected egg were positively related to the hypothesized difficulty of foreign egg puncturing. Potential advantages of thicker shells in common cuckoo eggs are discussed.     

新型多级冲击采样器切割粒径的标准粒子实验分析

大气溶胶对环境污染、气候变化以及人体健康有着重要的影响,大气溶胶的采集和分析已成为当前大气环境研究领域中的一个重要课题.论述的新型多级冲击采样器能够实现大气溶胶颗粒物按空气动力学粒径的大小7级分离采集,提供大致均匀的平面样品以进行后续的物理、化学分析,同时保证各分级切割粒径的稳定性.利用振动孔溶胶发生器产生均匀、粒径大致相同、单分散相的1.5～17μm空气动力学粒径标准粒子,对新型多级冲击采样器前三级的切割粒径和收集效率进行鉴定性分析实验,结果表明,能够满足对大气溶胶颗粒物分级采集的要求.