Can the study of nitrogen isotopic composition in size-segregated aerosol nitrate and ammonium be used to investigate atmospheric processing mechanisms?

Atmospheric fixed-nitrogen deposition can contribute to eutrophication in coastal and estuarine waters. Stable nitrogen isotope data can provide important information regarding the sources and processing of atmospheric fixed-nitrogen species and is thus important in controlling eutrophication. Size-segregated aerosol samples were collected from two coastal sites: Weybourne, England and Mace Head, Ireland and also aboard the RRS Challenger in the Eastern Atlantic Ocean. Aerosol concentrations of ammonium and nitrate were determined prior to δ¹⁵N isotopic analysis. The isotopic enrichment factor, ε, was calculated for both the species by subtracting the respective δ¹⁵N values of the coarse-mode fraction (>1 μm diameter) from those of the fine-mode fraction (<1 μm diameter). Variations in this parameter were observed as weak functions of the percentage of each species in the coarse mode and of meteorological condition. As a result, the presence of two different size-shift processes (dissociation/gas scavenging and dissolution/coagulation) is proposed, consistent with similar arguments based upon major-ion data obtained from the same suite of samples. Dissolution/coagulation processes appear to exhibit negative isotopic enrichment factors whereas dissociation/gas scavenging processes appear to exhibit positive enrichment factors, suggesting that they may be reversible and thermodynamically driven. In offshore-flowing air masses just entering the marine environment, transferral of nitrate to the coarse mode by initial dissociation of NH₄NO₃ followed by scavenging of the HNO₃ produced appears to be significantly more important than in samples of onshore, marine dominated air. In contrast, ammonium appears to be transferred to the coarse mode during offshore flow largely via the dissolution and coagulation of aerosol ammonium, nitrate and sulphate-containing species. During onshore flow, the uptake of gaseous NH₃, arising from the continued dissociation of NH₄NO₃, seems to become increasingly important.     

Oil Contamination in Ogoniland, Niger Delta

The study shows extensive oil contamination of rivers, creeks, and ground waters in Ogoniland, Nigeria. The levels found in the more contaminated sites are high enough to cause severe impacts on the ecosystem and human health: extractable petroleum hydrocarbons (EPHs) (>10-C40) in surface waters up to 7420 μg L⁻¹, drinking water wells show up to 42 200 μg L⁻¹, and benzene up to 9000 μg L⁻¹, more than 900 times the WHO guidelines. EPH concentrations in sediments were up to 17 900 mg kg⁻¹. Polycyclic aromatic hydrocarbons concentrations reached 8.0 mg kg⁻¹, in the most contaminated sites. The contamination has killed large areas of mangroves. Although the natural conditions for degradation of petroleum hydrocarbons are favorable with high temperatures and relatively high rainfall, the recovery of contaminated areas is prevented due to the chronic character of the contamination. Oil spills of varying magnitude originates from facilities and pipelines; leaks from aging, dilapidated, and abandoned infrastructure; and from spills during transport and artisanal refining of stolen oil under very primitive conditions.

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Size partitioning of particulate inorganic nitrogen species between the fine and coarse mode ranges and its implication to their deposition on the surface ocean

In order to discuss the dry deposition fluxes of atmospheric fixed nitrogen species, observations of aerosol chemistry including nitrate (NO₃^?) and ammonium (NH₄⁺) were conducted at two islands, Rishiri Island and Sado Island, over the Sea of Japan. Although the atmospheric concentrations of particulate NH₄⁺–N showed higher values than those of particulate NO₃^?–N at both sites, the dry deposition fluxes of the particulate NO₃^?–N were estimated to be higher than those of the particulate NH₄⁺–N. This was caused by the difference of particle sizes between the particulate NO₃^? and NH₄⁺; NH₄⁺ was almost totally contained in fine particles (d < 2.5 μm) with smaller deposition velocity, whereas NO₃^? was mainly contained in coarse particles (d > 2.5 μm) with greater deposition velocity. Fine mode NO₃^? was strongly associated with fine mode sea-salt and mineral particles, of which higher concentrations shifted the size of particulate NO₃^? toward the fine mode range. This size shift would decrease the dry deposition flux of the fixed nitrogen species on coastal waters and accelerate atmospheric transport of them to the remote oceanic areas.     

Evidence of Large-Scale Chronic Eutrophication in the Great Barrier Reef: Quantification of Chlorophyll a Thresholds for Sustaining Coral Reef Communities

Long-term monitoring data show that hard coral cover on the Great Barrier Reef (GBR) has reduced by >70 % over the past century. Although authorities and many marine scientists were in denial for many years, it is now widely accepted that this reduction is largely attributable to the chronic state of eutrophication that exists throughout most of the GBR. Some reefs in the far northern GBR where the annual mean chlorophyll a (Chl a) is in the lower range of the proposed Eutrophication Threshold Concentration for Chl a (~0.2–0.3 mg m⁻³) show little or no evidence of degradation over the past century. However, the available evidence suggests that coral diseases and the crown-of-thorns starfish will proliferate in such waters and hence the mandated eutrophication Trigger values for Chl a (~0.4–0.45 mg m⁻³) will need to be decreased to ~0.2 mg m⁻³ for sustaining coral reef communities.     

Valuation of ecotoxicological impacts from tributyltin based on a quantitative environmental assessment framework

In the scientific literature, few valuations of biodiversity and ecosystem services following the impacts of toxicity are available, hampered by the lack of ecotoxicological documentation. Here, tributyltin is used to conduct a contingent valuation study as well as cost–benefit analysis (CBA) of measures for improving the environmental status in Swedish coastal waters of the Baltic Sea. Benefits considering different dimensions when assessing environmental status are highlighted and a quantitative environmental assessment framework based on available technology, ecological conditions, and economic valuation methodology is developed. Two scenarios are used in the valuation study: (a) achieving good environmental status by 2020 in accordance with EU legislation (USD 119 household⁻¹ year⁻¹) and (b) achieving visible improvements by 2100 due to natural degradation (USD 108 household⁻¹ year⁻¹) during 8 years. The later scenario was used to illustrate an application of the assessment framework. The CBA results indicate that both scenarios might generate a welfare improvement.

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Assessing reference conditions according to the European Water Framework Directive using modelling and analysis of historical data: an example from Randers Fjord,Denmark

The European Water Framework Directive (WFD) requires the definition of reference conditions, i.e. pristine conditions, for all surface waters. As the present state of Danish coastal waters cannot be referred to as pristine, reference conditions have to be assessed by analysis of historical data or by the use of models. Using Randers Fjord as an example, the aim of this work was i) to demonstrate possibilities and restrictions of assessing reference conditions by historical data and by modelling; and ii) to demonstrate how ecological conditions have changed along with eutrophication. The ample historical data from Randers Fjord allowed us to assess reference conditions with respect to benthic macrophytes and benthic fauna. Models of varying complexity enabled us to assess reference conditions for nutrients, chlorophyll a, Secchi depth, and eelgrass. We conclude that models can be a useful supplement to assess reference conditions, though they are presently restricted by the lack of quantitative links between eutrophication and species composition.     

Improving Oxygen Conditions in the Deeper Parts of Bornholm Sea by Pumped Injection of Winter Water

Vertical diffusivity and oxygen consumption in the basin water, the water below the sill level at about 59 m depth, have been estimated by applying budget methods to monitoring data from hydrographical stations BY4 and BY5 for periods without water renewal. From the vertical diffusivity, the mean rate of work against the buoyancy forces below 65 m depth is estimated to about 0.10 mW m⁻². This is slightly higher than published values for East Gotland Sea. The horizontally averaged vertical diffusivity κ can be approximated by the expression κ = a₀N⁻¹ where N is the buoyancy frequency and a₀ ≈ 1.25 × 10⁻⁷ m² s⁻², which is similar to values for a₀ used for depths below the halocline in Baltic proper circulation models for long-term simulations. The contemporary mean rate of oxygen consumption in the basin water is about 75 g O₂ m⁻² year⁻¹, which corresponds to an oxidation of 28 g C m⁻² year⁻¹. The oxygen consumption in the Bornholm Basin doubled from the 1970s to the 2000s, which qualitatively explains the observed increasing frequency and vertical extent of anoxia and hypoxia in the basin water in records from the end of the 1950s to present time. A horizontally averaged vertical advection–diffusion model of the basin water is used to calculate the effects on stratification and oxygen concentration by a forced pump-driven vertical convection. It is shown that the residence time of the basin water may be reduced by pumping down and mixing the so-called winter water into the deepwater. With the present rate of oxygen consumption, a pumped flux of about 25 km³ year⁻¹ would be sufficient to keep the oxygen concentration in the deepwater above 2 mL O₂ L⁻¹.     

Consequences of nitrate leaching following stem-only harvesting of Swedish forests are dependent on spatial scale

Short-term increases in soil solution nitrate (NO₃⁻) concentration are often observed after forest harvest, even in N-limited systems. We model NO₃⁻ leaching below the rooting zone as a function of site productivity. Using national forest inventories and published estimates of N attenuation in rivers and the riparian zone, we estimate effects of stem-only harvesting on NO₃⁻ leaching to groundwater, surface waters and the marine environment. Stem-only harvesting is a minor contributor to NO₃⁻ pollution of Swedish waters. Effects in surface waters are rapidly diluted downstream, but can be locally important for shallow well-waters as well as for the total amount of N reaching the sea. Harvesting adds approximately 8 Gg NO₃-N to soil waters in Sweden, with local concentrations up to 7 mg NO₃-N l⁻¹. Of that, ∼3.3 Gg reaches the marine environment. This is ∼3% of the overall Swedish N load to the Baltic.     

Water and nitrate fluxes at a forest site in the North Tyrolean Limestone Alps

The water balance for the site Mühleggerköpfl in the North Tyrolean Limestone Alps has been established to a soil depth of 50 cm. The evaporation amounts to 42% and deep percolation is 58 % of the precipitation. The surface runoff was negligible and therefore the according nitrate fluxes as well. Soil water analysis revealed mean nitrate concentrations of 3 to 15 mg NO₃ L⁻¹, depending on soil depth. The nitrate concentrations at 50 cm soil depth and the associated percolation rates led to NO₂ ⁻N outputs of 15.9 kg NO₃ ⁻N ha⁻¹ in the year 1999 and 7.9 kg NO₃ ^∼N ha⁻¹ in the year 2000.

     

Land-use and agriculture in Denmark around year 1900 and the quest for EU Water Framework Directive reference conditions in coastal waters

The EU Water Framework Directive (WFD) aims to protect the ecological status of coastal waters. To establish acceptable boundaries between good and moderate ecological status, the WFD calls for reference conditions practically undisturbed by human impact. For Denmark, the nitrogen (N) concentrations present around year 1900 have been suggested to represent reference conditions. As the N load of coastal waters relates closely to runoff from land, any reduction in load links to agricultural activity. We challenge the current use of historical N balances to establish WFD reference conditions and initiate an alternative approach based on parish-level land-use statistics collected 1896/1900 and N concentrations in root zone percolates from experiments with year 1900-relevant management. This approach may be more widely applicable for landscapes with detailed historic information on agricultural activity. Using this approach, we find an average N concentration in root zone percolates that is close to that of current agriculture. Thus, considering Danish coastal waters to be practically unaffected by human activity around year 1900 remains futile as 75% of the land area was subject to agricultural activity with a substantial potential for N loss to the environment. It appears unlikely that the ecological state of coastal waters around year 1900 may serve as WFD reference condition.     

Sustainable farming practices of the Chinese mitten crab (<Emphasis Type="Italic">Eriocheir sinensis)</Emphasis> around Hongze Lake,lower Yangtze River Basin,China

Results of a survey of 156 Chinese mitten crab (Eriocheir sinensis) grow-out farms around Hongze Lake (118.48–118.72°E; 33.36–33.38°N) are reported. Area farmed has remained relatively unchanged but production (59 932 t in 2012) increased steadily over the last 7 years, indicative of the viability and sustainability of the farming system that has gradually replaced intensive Chinese major carp polyculture around Hongze Lake. Results showed that production range was 135–2400 kg ha⁻¹ cycle⁻¹ (mean 1144 ± 34). Crab yields correlated linearly to stocking density and conformed to a normal distribution curve, with 66.7 % of farms yielding 900 kg ha⁻¹ cycle⁻¹ or more. Yield was negatively correlated to pond size and capture size (p < 0.01), and farms with macrophyte coverage rate lower than 30 % of water surface were significantly (p < 0.05) lower than those exceeding 30 %.

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Assessing the steady-state [·NO<Subscript>2</Subscript>] in environmental samples

Based on available literature data of [NO₂ ⁻], steady-state [·OH], and ·OH generation rate upon nitrate photolysis in environmental aqueous samples under sunlight, the steady-state [·NO₂], could be calculated. Interestingly, one to two orders of magnitude more ·NO₂ would be formed in photochemical processes in atmospheric water droplets compared to transfer from the gas phase. The relative importance of nitrite oxidation compared to nitrate photolysis as an ·NO₂ source would be higher in atmospheric than in surface waters. The calculated levels of ·NO₂ could lead to substantial transformation of phenol into nitrophenols in both atmospheric and surface waters.     

Variation of wet deposition chemistry in Sequoia National Park,California

Sequoia National Park has monitored wet deposition chemistry in conjunction with the National Atmospheric Deposition Program and National Trends Network (NADP/NTN), on a weekly basis since July, 1980. Annual deposition of H, NO₃ and SO₄ (0.045, 3.6, and 3.9 kg ha⁻¹ a⁻¹, respectively) is relatively low compared to that measured in the eastern United States, or in the urban Los Angeles and San Francisco areas. Weekly ion concentrations are highly variable. Maximum concentrations of 324,162, and 156 μeq ol⁻¹ of H, NO₃ and SO₄ have been recorded for one low volume summer storm (1.4 mm). Summer concentrations of NO₃ and SO₄ average two and five times higher, respectively, than concentrations reported for remote areas in the world. There is considerable variability in the ionic concentration of low volume samples, and much less variability in moderate and high volume samples.     

Seasonal variations in atmospheric SOx and NOy species in the adirondacks

This paper reports the results of over 2 years of measurements of several of the species comprising atmospheric SO_x (=SO₂+SO₄²⁻) and NO_y (=NO+NO₂ + PAN + HNO₃+NO₃⁻+ organicnitrates + HONO + 2N₂O₅ …) at Whiteface Mountain, New York. Continuous real-time measurements of SO₂ and total gaseous NO_y provided data for about 50% and 65% of the period, respectively, and 122 filter pack samples were obtained for HNO₃, SO₂ and aerosol SO₄²⁻, NO₃⁻, H⁺ and NH₄⁺. Concentrations of SO₂ and NO_y were greatest in winter, whereas concentrations of the reaction products SO₄²⁻ and HNO₃were greatest in summer. The seasonal variation in SO₄²⁻ was considerably more pronounced than that of HNO₃and the high concentrations of SO₄²⁻ aerosol present in summer were also relatively more acidic than SO₄²⁻ aerosol in other seasons. As a result, SO₄²⁻ aerosol was the predominant acidic species present in summer, HNO₃was predominant in other seasons. Aerosol NO₃⁻ concentrations were low in all seasons and appeared unrelated to simultaneous NO_y and HNO₃concentrations. These data are consistent with seasonal variations in photochemical oxidation rates and with existing data on seasonal variations in precipitation composition. The results of this study suggest that emission reductions targeted at the summer season might be a cost-effective way to reduce deposition of S species, but would not be similarly cost-effective in reducing deposition of N species. kwAcid deposition, seasonal variation, sulfate, nitrate, nitric acid, sulfur dioxide, oxides of nitrogen, hydrogen peroxide, ozone, air pollution, Adirondack Mountains     

Atmospheric deposition of nitrogen emitted in the Metropolitan Area of Buenos Aires to coastal waters of de la Plata River

The Metropolitan Area of Buenos Aires (MABA) is the third mega-city in Latin America. Atmospheric N emitted in the area deposits to coastal waters of de la Plata River. This study describes the parameterizations included in DAUMOD-RD (v.3) model to evaluate concentrations of nitrogen compounds (nitrogen dioxide, gaseous nitric acid and nitrate aerosol) and their total (dry and wet) deposition to a water surface. This model is applied to area sources and CALPUFF model to point sources of NO_x in the MABA. The models are run for 3 years of hourly meteorological data, with a spatial resolution of 1 km². Mean annual deposition is 69, 728 kg-N year^?1 over 2 339 km² of river. Dry deposition contributions of N-NO₂, N-HNO₃ and N-NO₃^? to this value are 44%, 22% and 20%, respectively. Wet deposition of N-HNO₃ and N-NO₃^? represents 3% and 11% of total annual value, respectively. This very low contribution results from the rare occurrence of rainy hours with wind blowing from the city to the river. Monthly dry deposition flux estimated for coastal waters of MABA varies between 7 and 13 kg-N km^?2 month^?1. These results are comparable to values reported for other coastal zones in the world.     

Modeling wintertime particulate matter formation in central California

A wintertime episode during the 2000 California Regional PM Air Quality Study (CRPAQS) was simulated with the air quality model CMAQ–MADRID. Model performance was evaluated with 24-h average measurements available from CRPAQS. Modeled organic matter (OM) was dominated by emissions, which were probably significantly under-represented, especially in urban areas. In one urban area, modeled daytime nitrate concentrations were low and evening concentrations were high. This diurnal profile was not explained by the partition of nitrate between the gas and particle phases, because gaseous nitric acid concentrations were low compared to PM nitrate. Both measured and simulated nitrate concentrations aloft were lower than at the surface at two tower locations during this episode. Heterogeneous reactions involving NO₃ and N₂O₅ accounted for significant nitrate production in the model, resulting in a nighttime peak. The sensitivity of PM nitrate to precursor emissions varied with time and space. Nitrate formation was on average sensitive to NO_x emissions. However, for some periods at urban locations, reductions in NO_x caused the contrary response of nitrate increases. Nitrate was only weakly sensitive to reductions in anthropogenic VOC emissions. Nitrate formation tended to be insensitive to the availability of ammonia at locations with high nitrate, although the spatial extent of the nitrate plume was reduced when ammonia was reduced. Reductions in PM emissions caused OM to decrease, but had no effect on nitrate despite the role of heterogeneous reactions. A control strategy that focuses on NO_x and PM emissions would be effective on average, but reductions in VOC and NH₃ emissions would also be beneficial for certain times and locations.     

A New Phosphorus Paradigm for the Baltic Proper

The external phosphorus (P) loading has been halved, but the P content in the water column and the area of anoxic bottoms in Baltic proper has increased during the last 30 years. This can be explained by a temporary internal source of dissolved inorganic phosphorus (DIP) that is turned on when the water above the bottom sediment becomes anoxic. A load-response model, explaining the evolution from 1980 to 2005, suggests that the average specific DIP flux from anoxic bottoms in the Baltic proper is about 2.3 g P m⁻² year⁻¹. This is commensurable with fluxes estimated in situ from anoxic bottoms in the open Baltic proper and from hydrographic data in the deep part of Bornholm Basin. Oxygenation of anoxic bottoms, natural or manmade, may quickly turn off the internal P source from anoxic bottoms. This new P-paradigm should have far-reaching implications for abatement of eutrophication in the Baltic proper.

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Application of 15N–18O double stable isotope tracer technique in an agricultural nonpoint polluted river of the Yangtze Delta Region

One strategy to combat nitrate (NO₃-N) contamination in rivers is to understand its sources. NO₃-N sources in the East Tiaoxi River of the Yangtze Delta Region were investigated by applying a ¹⁵N–¹⁸O dual isotope approach. Water samples were collected from the main channel and from the tributaries. Results show that high total N and NO₃-N are present in both the main channel and the major tributaries, and NO₃-N was one of the most important N forms in water. Analysis of isotopic compositions (δ ¹⁸O, δD) of water suggests that the river water mainly originated from three tributaries during the sampling period. There was a wide range of δ ¹⁵N-NO₃ (?1.4 to 12.4 ‰) and a narrow range of δ ¹⁸O-NO₃ (3.7 to 9.0 ‰) in the main channel waters. The δ ¹⁵N and δ ¹⁸O-NO₃ values in the upper, middle, and lower channels along the river were shifted as 8.2, 3.5, and 9.5 ‰, and 9.0, 4.2, and 6.0 ‰, respectively. In the tributary South Tiao, the δ ¹⁵N and δ ¹⁸O-NO₃ values were as high as 9.5 and 7.0 ‰, while in the tributaries Mid Tiao and North Tiao, NO₃-N in most of the samples had relatively low δ ¹⁵N and δ ¹⁸O-NO₃ values from 2.3 to 7.5 ‰ and 4.7 to 7.0 ‰, separately. Our results also suggest that the dual isotope approach can help us develop the best management practice for relieving NO₃-N pollution in the rivers at the tributary scale.     

Nitrate removal under different ecological remediation measures in Taihu Lake: a 15 N mass-balance approach

Ecological remediation is an important measure for the protection of lake water quality in removing nutrients, such as nitrate (NO₃ ^?). In this study, four bioremediation processes (bare sediment, immobilized nitrogen cycling bacteria (INCB) added, Elodea nuttallii added, E. nuttallii-INCB assemblage) were operated at a lab to elucidate the effect of macrophyte appearance and INCB addition on NO₃ ^? removal and achieve the optimal processes for biomediation. ¹⁵?N-NO₃ solution was added to microcosms to identify the key nitrogen transformation processes responsible for NO₃ ^? removal. Results showed that nitrate removal was significantly enhanced after the addition of INCB and E. nuttallii. In the treatments with INCB added, E. nuttallii added, and INCB and E. nuttallii-INCB assemblage, nitrate removal ratio achieved 94.74, 98.76, and 99.15 %, respectively. In contrast, only 23.47 % added nitrate was removed in the control. Plant uptake and denitrification played an important role in nitrogen removal. The water quality was substantially improved by the addition of INCB and macrophyte that can accelerate denitrification and promote nitrogen assimilation of plants. The results indicated that plant uptake and microbial denitrification were key processes for nitrate removal.     

Changes in soil inorganic nitrogen as related to atmospheric nitrogenous pollutants in southern California

The deposition of nitrogenous pollutants has serious implications for ecosystem function and stability. Research in temperate ecosystems has indicated a wide range of ecological responses, yet very little is known about arid ecosystems. In this study, measurements of atmospheric and soil concentrations of the plant-available NO^-₃ and NH⁺₄ were evaluated to identify a potential gradient in nitrogen (N) deposition. The evaluations were conducted in coastal sage scrub, a semi-arid vegetation type native to the lower elevations of southern California.The summer atmospheric concentrations of nitrate (NO^-₃) and ammonium (NH⁺₄) were determined at five locations on the Perris Plain of southern California. The atmospheric influences varied from direct interception of pollution generated in the Los Angeles Basin at the northern end of the gradient to a site 70 km south lacking any direct Los Angeles influence. The summer atmospheric concentrations of NO^-₃ varied more than three-fold along the gradient. Ammonium concentrations followed a similar pattern, but the gradient was less steep. Winter concentrations were very low for both compounds. The summer soil surface NO^-₃ concentrations were near the detection limits at low pollution sites but in the range of 50–60 μg N g^-1 soil under highly polluted conditions. Wet deposition was found to be a minor contributor of plant-available N, suggesting that dry deposition may be a consequential source of plant-available N.The detection of significant changes in inorganic, plant-available N in the upper layer of soils is enhanced by the unique environmental conditions and vegetation of southern California. This study suggests that the coastal sage scrub ecosystem is experiencing significant changes in N fertility that may contribute to changes in plant species composition. The data also show that this semi-arid ecosystem provides a unique opportunity to assess many physical, chemical and biological responses to dry deposition alone.