Modelling the dynamic air-water-sediment coupled fluxes and occurrence of polychlorinated biphenyls in a high altitude lake

The BIODEP model in terms of atmosphere-lake interactions was developed. The model was applied to an oligotrophic, dimictic high altitude lake (Lake Redo, Pyrenees) for a range of polychlorinated biphenyl (PCB) congeners. High altitude lakes, which receive their contaminant inputs uniquely from the atmosphere through long-range atmospheric transport, provide ideal controlled environments for the study of the interactions between atmospheric depositional and water column biogeochemical processes. The BIODEP model was able to predict dissolved water concentrations and PCB accumulation in the lake sediment within a factor of 2. This shows that the BIODEP model captures the essential processes driving the sink of POPs in high altitude lakes and that POP occurrence in the lake is driven by direct atmospheric inputs with limited influence from the watershed. An important seasonal variability in water column concentrations is predicted which should have important implications in sampling strategies. Furthermore, it is shown that diffusive air-water exchange dominated the PCB dynamics in the lake, especially for the less chlorinated biphenyls.     

Variability and reliability of POP concentrations in multiple breast milk samples collected from the same mothers

Risk assessment of infant using a realistic persistent organic pollutant (POP) exposure through breast milk is essential to devise future regulation of POPs. However, recent investigations have demonstrated that POP levels in breast milk collected from the same mother showed a wide range of variation daily and monthly. To estimate the appropriate sample size of breast milk from the same mother to obtain reliable POP concentrations, breast milk samples were collected from five mothers living in Japan from 2006 to 2012. Milk samples from each mother were collected 3 to 6 times a day through 3 to 7 days consecutively. Food samples as the duplicated method were collected from two mothers during the period of breast milk sample collection. Those were employed for POP (PCBs, DDTs, chlordanes, and HCB) analysis. PCB concentrations detected in breast milk samples showed a wide range of variation which was maximum 63 and 60% of relative standard deviation (RSD) in lipid and wet weight basis, respectively. The time course trend of those variations among the mothers did not show any typical pattern. A larger amount of PCB intake through food seemed to affect 10 h after those concentrations in breast milk in lipid weight basis. Intraclass correlation coefficient (ICC) analyses indicated that the appropriate sample size for good reproducibility of POP concentrations in breast milk required at least two samples for lipid and wet weight basis.     

Evaluation of hydrochar efficiency for simultaneous removal of diclofenac and ibuprofen from aqueous system using surface response methodology

Environmental Science and Pollution Research - Pharmaceutically active compounds like diclofenac (DFS), ibuprofen (IBP), and other drugs that persist in the environment are listed as emerging...     

PCB in soils and estimated soil-air exchange fluxes of selected PCB congeners in the south of Sweden

PCB concentrations were studied in different soils to determine the spatial variation over a region of approximately 11 000 km(2). PCB congener pattern was used to illustrate the spatial differences, as shown by principal component analysis (PCA). The relationship to different soil parameters was studied. PCB concentrations in soil showed a large variation between sampling-areas with median concentrations ranging between 2.3 and 332 ng g(-1) (dw). Highest concentrations were found at two sites with sandy soils, one with extremely high organic carbon content. Both sites were located on the west coast of southern Sweden. Soils with similar soil textures (i.e. sandy silt moraine) did not show any significant differences in PCB concentrations. PCB congener composition was shown to differ between sites, with congener patterns almost site-specific. PCB in air and precipitation was measured and the transfer of chemicals between the soil and air compartments was estimated. Soil-air fugacity quotient calculations showed that the PCBs in the soil consistently had a higher fugacity than the PCBs in the air, with a median quotient value of 2.7. The gaseous fluxes between soil and air were estimated using standard modelling equations and a net soil-air flux estimated by subtracting bulk deposition from gaseous soil-air fluxes. It was shown that inclusion of vertical sorbed phase transport of PCBs in the soil had a large effect on the direction of the net soil-air exchange fluxes.     

A tunable diode laser system for ammonia flux measurements over multiple plots

This paper reports on the field testing of a tunable diode laser trace gas analyzer system for micrometeorological monitoring of ammonia fluxes. This system uses infrared absorption spectroscopy to measure atmospheric ammonia concentrations and the fluxgradient method to relate the measured concentration gradient to a flux of ammonia. For the field tests, we monitored ammonia fuxes over three plots receiving different manure applications. Each plot was sampled for 15 or 30 min of each hour, producing a high-temporal resolution data set. Analysis of the system response showed that ammonia adsorption to the tubing walls was greatly reduced by the system design and did not interfere with the flux measurement.     

Correction to: Evaluation of hydrochar efficiency for simultaneous removal of diclofenac and ibuprofen from aqueous system using surface response methodology

Environmental Science and Pollution Research - The original publication of this paper contain typographical mistakes.     

POP bioaccumulation in macroinvertebrates of alpine freshwater systems

This study serves to investigate the uptake of POPs in the different trophic levels (scrapers, collectors, predators, shredders) of macroinvertebrate communities sampled from a glacial and a non-glacial stream in the Italian Alps. The presented results show that the contaminant concentrations in glacial communities are generally higher compared to those from non-glacial catchments, highlighting the importance of glaciers as temporary sinks of atmospherically transported pollutants. Moreover, the data also suggests that in mountain systems snow plays an important role in influencing macroinvertebrate contamination. The main chemical uptake process to the macroinvertebrates is considered to be bioconcentration from water, as similar contaminant profiles were observed between the different trophic levels. The role of biomagnification/bioaccumulation is thought to be absent or negligible. The enrichment of chemicals observed in the predators is likely to be related to their greater lipid content compared to that of other feeding groups.     

Evaluation of an urban NMHC emission inventory by measurements and impact on CTM results

This paper presents an evaluation of the consistency of an urban state-of-the-art hydrocarbon (HC) emission inventory. The evaluation was conducted through the comparison of this inventory with hourly HC measurements during two summer months in the centre of Marseille, on the Mediterranean French coast. Factors of under or overestimation could be calculated for each compound on the basis of a systematic HC to HC ratio analysis. These results, associated with a deep analysis of the speciation profiles, show that most of the common and highly concentrated hydrocarbons (such as butanes) are too much predominant in the emission speciation, while the heavy and less common species (branched alkanes, substituted aromatics) are under-represented in the inventory. The urban diffuse sources appear here as one critical point of the inventories. The disagreements were shown to have a strong incidence on the representation of the air mass reactivity. In a last step, the identified uncertainties in emissions were implemented in an air-quality model for sensitivity studies. It was shown that the observed biases in the inventory could affect the regional ozone production, with a probable impact on ozone peaks of 2–10 ppbv over the area.     

Quantifying simultaneous fluxes of ozone, carbon dioxide and water vapor above a subalpine forest ecosystem

Assessing the long-term exchange of trace gases and energy between terrestrial ecosystems and the atmosphere is an important priority of the current climate change research. In this regard, it is particularly significant to provide valid data on simultaneous fluxes of carbon, water vapor and pollutants over representative ecosystems. Eddy covariance measurements and model analyses of such combined fluxes over a subalpine coniferous forest in southern Wyoming (USA) are presented. While the exchange of water vapor and ozone are successfully measured by the eddy covariance system, fluxes of carbon dioxide (CO(2)) are uncertain. This is established by comparing measured fluxes with simulations produced by a detailed biophysical model (FORFLUX). The bias in CO(2) flux measurements is partially attributed to below-canopy advection caused by a complex terrain. We emphasize the difficulty of obtaining continuous long-term flux data in mountainous areas by direct measurements. Instrumental records are combined with simulation models as a feasible approach to assess seasonal and annual ecosystem exchange of carbon, water and ozone in alpine environments. The viability of this approach is demonstrated by: (1) showing the ability of the FORFLUX model to predict observed fluxes over a 9-day period in the summer of 1996; and (2) applying the model to estimate seasonal dynamics and annual totals of ozone deposition and carbon, and water vapor exchange at our study site. Estimated fluxes above this subalpine ecosystem in 1996 are: 195 g C m(-2) year(-1) net ecosystem production, 277 g C m(-2) year(-1) net primary production, 535 mm year(-1) total evapo-transpiration, 174 mm year(-1) canopy transpiration, 2.9 g m(-2) year(-1) total ozone deposition, and 1.72 g O(3) m(-2) year(-1) plant ozone uptake via leaf stomata. Given the large portion of non-stomatal ozone uptake (i.e. 41% of the total annual flux) predicted for this site, we suggest that future research of pollution-vegetation interactions should relate plant response to actively assimilated ozone by foliage rather than to total deposition. In this regard, we propose the Physiological Ozone Uptake Per Unit of Leaf Area (POUPULA) as a practical index for quantifying vegetation vulnerability to ozone damage. We estimate POUPULA to be 0.614 g O(3) m(-2) leaf area year(-1) at our subalpine site in 1996.     

Emission strengths for primary pollutants as estimated from an aircraft study of Hong Kong air quality

An aircraft study of air quality in the Hong Kong region during the fall of 1994 has allowed for an estimation of the daytime source strengths for CO and NO_y from the Hong Kong metropolitan center. Emission rate estimates for the Hong Kong urban plume for NO_y and CO were 5.4×10e(25) molecules s^-1 and 1.8×10e(26) molecules s^-1 as determined for the case study of 18 October. All emission rate estimates have uncertainties of a factor of 2. On one occasion a distinct plume emanating from Shenzhen in the People’s Republic of China was encountered. While plume delimitation was insufficient for source strength calculations, transect integrals did allow for a CO/NO_y ratio of about 16 to be determined. The CO/NO_y ratio for the Hong Kong urban plume was about 3.3. The difference in these ratios indicates differences in the overall combustion processes and efficiencies taking place within Hong Kong and the PRC.     

Deposition fluxes of PCDD/Fs in a reservoir system in northern Taiwan

In this study, polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) concentrations and depositions in ambient air, water column and sediment were measured at a coupled reservoir-watershed system in northern Taiwan. The atmospheric PCDD/F concentration measured in the vicinity of the reservoir ranged from 4.9 to 39 fg I-TEQ m⁻³ and the Asian dust storm in February accounted for the peak value, which corresponded to a total suspended particle concentration of 128 μg m⁻³. The atmospheric PCDD/F deposition ranged from 1.4 to 19 pg I-TEQ m⁻² d⁻¹, with higher deposition occurring during winter and spring (long-range transport events). During summer, when atmospheric deposition is lower, consecutive tropical cyclones (typhoons) bring heavy rainfall that enhances soil erosion and creates turbidity-driven intermediate flow. This results in significantly higher PCDD/F deposition in water column of the reservoir at 70 m water depth (179 pg I-TEQ m⁻² d⁻¹) than at 20 m (21 pg I-TEQ m⁻² d⁻¹) during typhoon event. The accumulation rate of PCDD/Fs (9.1 ng I-TEQ m⁻² y⁻¹) in the reservoir sediments (depth: 0-2 cm) was consistent with PCDD/F deposition obtained from water column (6.1 and 8.3 ng I-TEQ m⁻² y⁻¹); however, it is significantly higher when compared to the atmospheric deposition (2.0 ng I-TEQ m⁻² y⁻¹). Based on the mass balance between the measurements of atmospheric deposition and sinking particles in water column, around 54-74% of PCDD/F inputs into the reservoir were contributed by the catchment erosion during normal period. However, the PCDD/F input contributed by the enhanced catchment erosion significantly increased to 90% during intensive typhoon events.     

膜生物反应器同步硝化反硝化系统的研究

设计结构合理的膜生物反应器,驯化培养硝化污泥,复配反硝化细菌,构建了具有同步硝化反硝化功能且能去除COD的膜生物反应器系统.MLVSS的增高和污泥结构的改善为同步硝化反硝化提供条件.进水氨氮浓度在50 mg/L,MLVSS为8 g/L时,最佳HRT为4～6 h,气量控制在0.5 m3/h左右,TN去除率达80%以上.系统承受负荷变化范围0～0.36 kg N/(m3·d),TN去除率均能保持80%左右,COD去除率稳定在90%.系统投加粉末活性炭的方法可以改善污泥结构,进而减轻膜污染.在试验阶段内,添加了PAC的活性污泥MLVSS的高低对膜通量的影响不大,膜通量基本保持稳定.     

Comparison of manual and automated chambers for field measurements of N2O,CH4, CO2 fluxes from cultivated land

Chamber techniques can easily be applied to field trials with multiple small plots measuring carbon- and nitrogen-trace gas fluxes. Nevertheless, such chamber measurements are usually made weekly and rarely more frequently than once daily. However, automatic chambers do allow flux measurements on sub-daily time scales. It has been hypothesized that sub-daily measurements provide more reliable results, as diurnal variations are captured better compared to manual measurements. To test this hypothesis we compared automatic and manual measurements of N₂O, CO₂ and CH₄ fluxes from tilled and non-tilled plots of a rice–wheat rotation ecosystem over a non-waterlogged period. Our results suggest that both techniques, i.e., either manual or automatic chambers of N₂O and CO₂ emissions resulted in biased fluxes. The manual measurements were adequate to capture either day-to-day or seasonal dynamics of N₂O, CO₂ and CH₄ exchanges, but overestimated the cumulative N₂O and CO₂ emissions by 18% and 31%, respectively. This was due to neglecting temperature-dependent diurnal variations of C and N trace gas fluxes. However, the automatic measurements underestimated the cumulative emissions of N₂O and CO₂ by 22% and 17%, respectively. This underestimation resulted from chamber effects upon soil moisture during rainfall processes. No significant difference was detected between the two methods in CH₄ exchanges over the non-waterlogged soils. The bias of manual chambers may be significant when pronounced diurnal variations occur. The bias of automatic measurements can only be avoided/minimized if chamber positions are frequently changed and/or if chambers are automatically opened during rainfall events. We therefore recommend using automatic chambers together with continuous measurements of soil chamber moisture to allow for soil moisture correction of fluxes or to correct flux estimates as derived by manual chambers for possible diurnal variations.     

Screening of POP pollution by AChE and EROD activities in Zebra mussels from the Italian Great Lakes

The increase of ethoxyresorufin dealkylation (EROD) and the inhibition of acetylcholinesterase (AChE) as biomarkers have been commonly used in vertebrates for the persistent organic pollutants (POPs) biomonitoring of aquatic environments, but very few studies have been performed for invertebrates. Previous researches demonstrated the interference due to some chemicals on EROD and AChE activities of the freshwater bivalve Zebra mussel (Dreissena polymorpha) in laboratory and field studies, showing its possible use for the screening of POP effects. We investigated the contamination of the Italian sub-alpine great lakes (Maggiore, Lugano, Como, Iseo, Garda) by the biomarker approach on Zebra mussel specimens collected at 17 sampling sites with different morphometric characteristics and anthropization levels. Results showed a homogeneous contamination of AChE inhibitors in Lake Garda, Maggiore, Como and Iseo with values ranging from 0.5 to 3 nmol/min/mg proteins and with an average inhibition of about 66% to controls. The planar compounds pollution, able to activate the EROD activity, seems higher in some sampling stations of Lake Garda, Como and Iseo (2-4 pmol/min/mg proteins) than that measured in Lake Lugano (1.5-3 pmol/min/mg proteins). On the contrary, the enzyme activity in Lake Maggiore showed an interesting opposite effect of AhR-binding compounds and trace metals. Finally, the possible use of Zebra mussel specimens maintained at laboratory conditions as controls against the selection of the less polluted sampling site is discussed.     

Bioavailability of contaminants estimated from uptake rates into soil invertebrates

It is often argued that the concentration of a pollutant inside an organism is a good indicator of its bioavailability, however, we show that the rate of uptake, not the concentration itself, is the superior predictor. In a study on zinc accumulation and toxicity to isopods (Porcellio scaber) the dietary EC(50) for the effect on body growth was rather constant and reproducible, while the internal EC(50) varied depending on the accumulation history of the animals. From the data a critical value for zinc accumulation in P. scaber was estimated as 53 microg/g/wk. We review toxicokinetic models applicable to time-series measurements of concentrations in invertebrates. The initial slope of the uptake curve is proposed as an indicator of bioavailability. To apply the dynamic concept of bioavailability in risk assessment, a set of representative organisms should be chosen and standardized protocols developed for exposure assays by which suspect soils can be evaluated.     

Methane fluxes from tundra soils and snowpack in the maritime Antarctic

Methane fluxes were measured from three exposed tundra sites and four snowpack sites on the Fildes Peninsula in the maritime Antarctic in the summertime of 2002. The average fluxes at two normal tundra sites were −15.3 μg m⁻² h⁻¹ and −14.3 μg m⁻² h⁻¹, respectively. The fluxes from tundra site with fresh penguin dropping addition showed positive values with the average of 36.1 μg m⁻² h⁻¹, suggesting that the deposition of fresh droppings greatly enhanced CH₄ emissions from the poor Antarctic tundra during penguin breeding periods. The summertime variation in CH₄ flux was correlated with surface ground temperature and the precipitation. The correlation between the flux and PT₀, which is the product of the precipitation and surface ground temperature, was quite strong. The diurnal cycle of CH₄ flux from the tundra soils was not obtained due to local fluky weather conditions. The fluxes through four snowpack sites were also obtained by the vertical CH₄ concentration gradient and their average fluxes were −46.5 μg m⁻² h⁻¹, −28.2 μg m⁻² h⁻¹, −46.4 μg m⁻² h⁻¹ and −17.9 μg m⁻² h⁻¹, respectively, indicating that tundra soils under snowpack also consume atmospheric CH₄ in the maritime Antarctic; therefore these fluxes could constitute an important part of the annual CH₄ budget for Antarctic tundra ecosystem.     

Gaseous mercury fluxes from the forest floor of the Adirondacks

The flux of gaseous elemental mercury (Hg⁰) from the forest floor of the Adirondack Mountains in New York (USA) was measured numerous times throughout 2005 and 2006 using a polycarbonate dynamic flux chamber (DFC). The Hg flux ranged between −2.5 and 27.2 ng m⁻² h⁻¹ and was positively correlated with temperature and solar radiation. The measured Hg emission flux was highest in spring, and summer, and lowest in winter. During leaf-off periods, the Hg emission flux was highly dependent on solar radiation and less dependent on temperature. During leaf-on periods, the Hg emission flux was fairly constant because the forest canopy was shading the forest floor. Two empirical models were developed to estimate yearly Hg⁰ emissions, one for the leaf-off period and one for the leaf-on period. Using the U.S. EPA's CASTNET meteorological data, the cumulative estimated emission flux was approx. 7.0 μg Hg⁰ m⁻² year⁻¹.     

Dry deposition fluxes and deposition velocities of PAHs at an urban site in Turkey

Even though dry deposition and air–water exchange of semivolatile organic compounds (SOCs) are important for surfaces in and around the urban areas, there is still no generally accepted direct measurement technique for dry deposition. In this study, a modified water surface sampler (WSS) configuration, including a filter holder and an XAD-2 resin column, was employed to investigate the polycyclic aromatic hydrocarbon (PAH) dry deposition in an urban area. The measured total (particle+dissolved) PAH fluxes to the WSS averaged to be 34 960±16 540 ng m⁻² d⁻¹. Average particulate PAH flux, determined by analyzing the filter in the WSS, was about 8% of the total PAH flux. Temporal flux variations indicated that colder months (October–April) had the highest PAH fluxes. This increase could be attributed to the residential heating as well as meteorological effects including lower mixing height. A high volume air sampler was concurrently employed to collect ambient air concentrations. The average total (gas+particle) atmospheric PAH concentration (456±524 ng m⁻³) was within the range of previously measured values at different urban locations. PAH concentrations in urban areas are more than two orders of magnitude higher than those measured in pristine areas and this result may indicate that urban areas have major source sectors and greater deposition rates are expected near to these areas. The average contribution of particle phase was about 10% in total concentration. Simultaneous particulate phase dry deposition and ambient air samples were collected in this study. Then, particulate phase apparent dry deposition velocities were calculated using the fluxes and concentrations for each PAH compound and they ranged from 0.1 to 1.2 cm s⁻¹. These values are in good agreement with previously reported values.     

Nitrogen fluxes on an intensive investigation plot in the North Tyrolean limestone Alps

In the framework of this study, nitrogen fluxes on a limestone site are investigated. The major goals are the assessment of the nitrogen status, the estimation of the nitrogen budget and the evaluation of the nitrogen saturation. The investigation area, the intensive investigation plot and the research equipment are described.