Present limitations and future prospects of stable isotope methods for nitrate source identification in surface- and groundwater

Nitrate (NO₃⁻) contamination of surface- and groundwater is an environmental problem in many regions of the world with intensive agriculture and high population densities. Knowledge of the sources of NO₃⁻ contamination in water is important for better management of water quality. Stable nitrogen (δ¹⁵N) and oxygen (δ¹⁸O) isotope data of NO₃⁻ have been frequently used to identify NO₃⁻ sources in water. This review summarizes typical δ¹⁵N- and δ¹⁸O-NO₃⁻ ranges of known NO₃⁻ sources, interprets constraints and future outlooks to quantify NO₃⁻ sources, and describes three analytical techniques (“ion-exchange method”, “bacterial denitrification method”, and “cadmium reduction method”) for δ¹⁵N- and δ¹⁸O-NO₃⁻ determination. Isotopic data can provide evidence for the presence of dominant NO₃⁻ sources. However, quantification, including uncertainty assessment, is lacking when multiple NO₃⁻ sources are present. Moreover, fractionation processes are often ignored, but may largely constrain the accuracy of NO₃⁻ source identification. These problems can be overcome if (1) NO₃⁻ isotopic data are combined with co-migrating discriminators of NO₃⁻ sources (e.g. ¹¹B), which are not affected by transformation processes, (2) contributions of different NO₃⁻ sources can be quantified via linear mixing models (e.g. SIAR), and (3) precise, accurate and high throughput isotope analytical techniques become available.     

Point source influences on the carbon and nitrogen geochemistry of sediments in the Stockholm inner archipelago, Sweden

This study reports analyses of carbon and nitrogen content, and delta(15)N and delta(13)C in sediments of the H?ggarnsfj?rden Bay near Stockholm. Samples have been taken upstream, near, and downstream of a point source of processed leach water from a garbage dump. The surface sediment at the upstream and downstream sites has delta(15)N and delta(13)C close to the expected background of the area, even though a contribution from the leach water can be observed downstream of the point source. The sediment close to the outflow is strongly influenced by the carbon and nitrogen in the leach water.     

Intrinsic biodegradation potential of aromatic hydrocarbons in an alluvial aquifer--potentials and limits of signature metabolite analysis and two stable isotope-based techniques

Three independent techniques were used to assess the biodegradation of monoaromatic hydrocarbons and low-molecular weight polyaromatic hydrocarbons in the alluvial aquifer at the site of a former cokery (Flémalle, Belgium).Firstly, a stable carbon isotope-based field method allowed quantifying biodegradation of monoaromatic compounds in situ and confirmed the degradation of naphthalene. No evidence could be deduced from stable isotope shifts for the intrinsic biodegradation of larger molecules such as methylnaphthalenes or acenaphthene. Secondly, using signature metabolite analysis, various intermediates of the anaerobic degradation of (poly-) aromatic and heterocyclic compounds were identified. The discovery of a novel metabolite of acenaphthene in groundwater samples permitted deeper insights into the anaerobic biodegradation of almost persistent environmental contaminants. A third method, microcosm incubations with ¹³C-labeled compounds under in situ-like conditions, complemented techniques one and two by providing quantitative information on contaminant biodegradation independent of molecule size and sorption properties. Thanks to stable isotope labels, the sensitivity of this method was much higher compared to classical microcosm studies. The ¹³C-microcosm approach allowed the determination of first-order rate constants for ¹³C-labeled benzene, naphthalene, or acenaphthene even in cases when degradation activities were only small. The plausibility of the third method was checked by comparing ¹³C-microcosm-derived rates to field-derived rates of the first approach. Further advantage of the use of ¹³C-labels in microcosms is that novel metabolites can be linked more easily to specific mother compounds even in complex systems. This was achieved using alluvial sediments where ¹³C-acenaphthyl methylsuccinate was identified as transformation product of the anaerobic degradation of acenaphthene.     

Isotopic tracing of clear water sources in an urban sewer: A combined water and dissolved sulfate stable isotope approach

This paper investigates the potential of stable isotopes of both water (δD and ) and dissolved sulfate (δ³⁴S and ) for determining the origin and the amount of clear waters entering an urban sewer. The dynamics of various hydrological processes that commonly occur within the sewer system such as groundwater infiltration, rainwater percolation, or stormwater release from retention basins, can be readily described using water isotope ratios. In particular, stable water isotopes indicate that the relative volumes of infiltrated groundwater and sewage remain approximately constant and independent of wastewater flow rate during the day, thus demonstrating that the usual quantification of parasitic discharge from minimal nocturnal flow measurements can lead to completely erroneous results. The isotopic signature of dissolved sulfate can also provide valuable information about the nature of water inputs to the sewage flow, but could not be used in our case to quantify the infiltrating water. Indeed, even though the microbial activity had a limited effect on the isotopic composition of dissolved sulfate at the sampling sites investigated, the dissolved sulfate concentration in sewage was regulated by the formation of barite and calcium-phosphate mineral species. Sulfate originating from urine was also detected as a source using the oxygen isotopic composition of sulfate, which suggests that might find use as a urine tracer.     

An evaluation of teeth of ringed seals (Phoca hispida) from Greenland as a matrix to monitor spatial and temporal trends of mercury and stable isotopes

Total mercury (Hg) concentrations were measured in teeth of ringed seals from Qeqertarsuaq, central West Greenland (1982 to 2006) and Ittoqqortoormiit, central East Greenland (1986 to 2006). Stable isotopic ratios of carbon (¹³C/¹²C) and nitrogen (¹⁵N/¹⁴N) were determined as well to provide insights into diet variations between regions or through time. Mercury concentrations decreased the first years of life of the animals suggesting that Hg had been transferred from the mother to the foetus and newborn. The Hg concentrations in teeth were significantly lesser in ringed seals from central West Greenland compared to those from central East Greenland. Carbon and nitrogen stable isotopic values measured in the animals differed also significantly between the two regions. Increasing temporal trends of dental Hg concentrations between 1994 and 2006 were observed in ringed seals from both central West Greenland and central East Greenland. These increases were attributed to global changes in environmental Hg levels since no temporal trends in δ¹⁵N values were found to support the hypothesis of a diet shift over time. Furthermore, a decreasing temporal trend in δ¹³C values was observed in the teeth of seals from central East Greenland, and explained by a likely change over time towards more pelagic feeding habits; alternatively, the so-known Seuss effect was thought to be responsible for this decrease. Finally, it was concluded that the tooth of ringed seal was a good monitoring tissue to assess Hg trends.     

Fog drip and its relation to groundwater in the tropical seasonal rain forest of Xishuangbanna, Southwest China: a preliminary study

Rain, fog drip, shallow soil water and groundwater were collected for two years (2002-2003) for stable isotopic analysis, at a tropical seasonal rain forest site in Xshuangbanna, Southwest China. The fog drip water ranged from -30 to +27 per thousand in deltaD and -6.2 to +1.9 per thousand in delta(18)O, conforms to the equation deltaD=7.64delta(18)O+14.32, and was thought to contain water that has been evaporated and recycled terrestrial meteoric water. The rain was isotopically more depleted, and ranged from -94 to -45 per thousand in deltaD, and -13.2 to -6.8 per thousand in delta(18)O. The shallow soil water had a composition usually between those of the rain and fog drip, and was assumed to be a mixture of the two waters. However, the soil water collected in dry season appeared to contain more fog drip water than that collected in rainy season. The groundwater in both seasons had an isotopic composition similar to rainwater, suggesting that fog drip water does not play a significant role as a source of recharge for the groundwater. This groundwater was thought to be recharged solely by rainwater.     

Biodilution of heavy metals in a stream macroinvertebrate food web: evidence from stable isotope analysis

Analysis of carbon (delta13C) and nitrogen (delta15N) stable isotopes provides an increasingly important means of understanding the complex trophic structure of macroinvertebrate communities in streams. We coupled a stable isotope approach with a contaminant analysis of six metals (Pb, Ag, Zn, Hg, Cu, As) to trace the accumulation and dilution of metals from an abandoned mine across trophic levels of the benthic community in Ginzan Creek, Japan. The delta15N signature increased with trophic level, with mean increases of 4.70 per thousand from producers to primary consumers and 3.06 per thousand from primary to secondary consumers. Tissue Pb and Ag concentrations were negatively correlated with delta15N, indicating biodilution of both metals through the food web. Although macroinvertebrate taxon body mass was negatively correlated with tissue metal concentration at several sites, it did not increase with trophic level (as delta15N) in any of the sites, suggesting that changes in body mass were not the cause of biodilution. Our findings suggest invertebrates at higher trophic levels may exhibit increasingly efficient excretion of metals. Autotrophic epilithon (mean delta13C= -21.3 per thousand) had a much higher concentration of mined metals than did riparian vegetation (mean delta13C= -29.3 per thousand); nonetheless, a carbon-mixing model indicated that taxa feeding on autochthonous carbon sources did not accumulate more metal than allochthonous feeders. It is likely that the notably high metal concentration of allochthonous FPOM plays an important role in the trophic transfer of metals. Our data suggest the strong potential for stable isotope analysis to enhance our understanding of metal transfer through stream macroinvertebrate food webs.     

Trophic structure and mercury distribution in a Gulf of St. Lawrence (Canada) food web using stable isotope analysis

Even at low concentrations in the environment, mercury has the potential to biomagnify in food chains and reaches levels of concern in apex predators. The aim of this study was to relate the transfer of total mercury (THg) and methylmercury (MeHg) in a Gulf of St. Lawrence food web to the trophic structure, from primary consumers to seabirds, using stable nitrogen (δ¹⁵N) and carbon (δ¹³C) isotope analysis and physical environmental parameters. The energy reaching upper trophic level species was principally derived from pelagic primary production, with particulate organic matter (POM) at the base of the food chain. We developed a biomagnification factor (BMF) taking into account the various prey items consumed by a given predator using stable isotope mixing models. This BMF provides a more realistic estimation than when using a single prey. Lipid content, body weight, trophic level and benthic connection explained 77.4 and 80.7% of the variation in THg and MeHg concentrations, respectively in this food web. When other values were held constant, relationships with lipid and benthic connection were negative whereas relationships with trophic level and body weight were positive. Total Hg and MeHg biomagnified in this food web with biomagnification power values (slope of the relationship with δ¹⁵N) of 0.170 and 0.235, respectively on wet weight and 0.134 and 0.201, respectively on dry weight. Values of biomagnification power were greater for pelagic and benthopelagic species compared to benthic species whereas the opposite trend was observed for levels at the base of the food chain. This suggests that Hg would be readily bioavailable to organisms at the base of the benthic food chain, but trophic transfer would be more efficient in each trophic level of pelagic and benthopelagic food chains.     

Use of stable nitrogen isotope fractionation to estimate denitrification in small constructed wetlands treating agricultural runoff

Constructed wetlands (CWs) in the agricultural landscape reduce non-point source pollution through removal of nutrients and particles. The objective of this study was to evaluate if measurements of natural abundance of (15)NO(3)(-) can be used to determine the fate of NO(3)(-) in different types of small CWs treating agricultural runoff. Nitrogen removal was studied in wetland trenches filled with different filter materials (T1--sand and gravel; T3--mixture of peat, shell sand and light-weight aggregates; T8--barley straw) and a trench formed as a shallow pond (T4). The removal was highest during summer and lowest during autumn and winter. Trench T8 had the highest N removal during summer. Measurements of the natural abundance of (15)N in NO(3)(-) showed that denitrification was not significant during autumn/winter, while it was present in all trenches during summer, but only important for nitrogen removal in trench T8. The (15)N enrichment factors of NO(3)(-) in this study ranged from -2.5 to -5.9 per thousand (T3 and T8, summer), thus smaller than enrichment factors found in laboratory tests of isotope discrimination in denitrification, but similar to factors found for denitrification in groundwater and a large CW. The low enrichment factors compared to laboratory studies was attributed to assimilation in plants/microbes as well as diffusion effect. Based on a modified version of the method presented by Lund et al. [Lund LJ, Horne AJ, Williams AE, Estimating denitrification in a large constructed wetland using stable nitrogen isotope ratios. Ecol Engineer 2000; 14: 67-76], denitrification and assimilation were estimated to account for 53 to 99 and 1 to 47%, respectively, of the total N removal during summer. This method is, however, based on a number of assumptions, and there is thus a need for a better knowledge of the effect of plant uptake, microbial assimilation as well as nitrification on N isotopic fractionation before this method can be used to evaluate the contribution of dinitrification in CWs.     

Traffic pollution affects tree-ring width and isotopic composition of Pinus pinea

This study presents new evidence that radiocarbon, combined with dendrochronological and stable isotopes analysis in tree rings and needles, can help to better understand the influence of pollution on trees. Pinus pinea individuals, adjacent to main roads in the urban area of Caserta (South Italy) and exposed to large amounts of traffic exhaust since 1980, were sampled and the time-related trend in the growth residuals was estimated. We found a consistent decrease in the ring width starting from 1980, with a slight increase in δ¹³C value, which was considered to be a consequence of environmental stress. No clear pattern was identified in δ¹⁵N, while an increasing effect of the fossil fuel dilution on the atmospheric bomb-enriched ¹⁴C background was detected in tree rings, possibly as a consequence of the increase in traffic exhausts. Our findings suggested that radiocarbon is a very sensitive tool to investigate small-scale (i.e. traffic exhaust at the level crossing) and large-scale (urban area pollution) induced disturbances.     

Evaluating the utility of 15N and 18O isotope abundance analyses to identify nitrate sources: A soil zone study

¹⁵N and ¹⁸O isotope abundance analyses in nitrate (NO₃⁻) (expressed as δ¹⁵N-NO₃⁻ and δ¹⁸O-NO₃⁻ values respectively) have often been used in research to help identify NO₃⁻ sources in rural groundwater. However, questions have been raised over the limitations as overlaps in δ values may occur between N source types early in the leaching process. The aim of this study was to evaluate the utility of using stable isotopes for nitrate source tracking through the determination of δ¹⁵N-NO₃⁻ and δ¹⁸O-NO₃⁻ in the unsaturated zone from varying N source types (artificial fertiliser, dairy wastewater and cow slurry) and rates with contrasting isotopic compositions. Despite NO₃⁻ concentrations being often elevated, soil-water nitrate poorly mirrored the ¹⁵N content of applied N and therefore, δ¹⁵N-NO₃⁻ values were of limited assistance in clearly associating nitrate leaching with N inputs. Results suggest that the mineralisation and the nitrification of soil organic N, stimulated by previous and current intensive management, masked the cause of leaching from the isotopic prospective. δ¹⁸O-NO₃⁻ was of little use, as most values were close to or within the range expected for nitrification regardless of the treatment, which was attributed to the remineralisation of nitrate assimilated by bacteria (mineralisation-immobilisation turnover or MIT) or plants. Only in limited circumstances (low fertiliser application rate in tillage) could direct leaching of synthetic nitrate fertiliser be identified (δ¹⁵N-NO₃⁻ < 0‰ and δ¹⁸O-NO₃⁻ > 15‰). Nevertheless, some useful differences emerged between treatments. δ¹⁵N-NO₃⁻ values were lower where artificial fertiliser was applied compared with the unfertilised controls and organic waste treatments. Importantly, δ¹⁵N-NO₃⁻ and δ¹⁸O-NO₃⁻ variables were negatively correlated in the artificial fertiliser treatment (0.001 ≤ p ≤ 0.05, attributed to the varying proportion of fertiliser-derived and synthetic nitrate being leached) while positively correlated in the dairy wastewater plots (p ≤ 0.01, attributed to limited denitrification). These results suggest that it may be possible to distinguish some nitrate sources if analysing correlations between δ variables from the unsaturated zone. In grassland, the above correlations were related to N input rates, which partly controlled nitrate concentrations in the artificial fertiliser plots (high inputs translated into higher NO₃⁻ concentrations with an increasing proportion of fertiliser-derived and synthetic nitrate) and denitrification in the dairy wastewater plots (high inputs corresponded to more denitrification). As a consequence, nitrate source identification in grassland was more efficient at higher input rates due to differences in δ values widening between treatments.     

Identification and quantification of nitrogen removal in a rotating biological contactor by 15N tracer techniques

High autotrophic nitrogen removal rates of 858mg NL(-1) day(-1) or 1.55g Nm(-2) day(-1) were obtained in a lab-scale rotating biological contactor treating an ammonium rich influent. It was postulated that ammonium was removed as dinitrogen gas by a sequence of aerobic ammonium oxidation to nitrite taking place in the outer biofilm layer and anaerobic ammonium oxidation with nitrite as electron acceptor occuring in the deeper biofilm layer. Chemical evidence for anaerobic ammonium oxidation within intact biofilm sludge from a lab-scale rotating biological contactor could be provided, without direct identification of responsible organisms catalysing this reaction. 15N tracer techniques were used for identification and quantification of nitrogen transformations. In batch tests with biofilm sludge at dissolved oxygen concentrations lower than 0.1mgL(-1), ammonium and nitrite did react in a stoichiometric ratio of 1:1.43 thereby forming dinitrogen. 15N isotope dilution calculations revealed that anaerobic ammonium oxidation was the major nitrogen transformation leading to concomitant ammonium and nitrite removal. Isotopic analysis of the produced biogas showed that both ammonium-N and nitrite-N were incorporated in N(2).     

我国城市交通问题存在根源分析和解决措施

论述了我国城市交通存在的具体问题和面临的挑战,就城市问题存在的根源性做了重点分析,并且提出了解决城市交通问题的措施,最后提出了应该贯彻“可持续发展城市交通系统”的理念。     

Engineering a lignocellulosic biosorbent - Coir pith for removal of cesium from aqueous solutions: Equilibrium and kinetic studies

A novel method of engineering lignocellulosic biosorbent- coir pith (CP) by incorporation of nickel hexacyanoferrate (NiHCF), also referred to as Prussian blue analogue (PBA) inside its porous matrix is reported. Structural characterization confirmed the successful synthesis of NiHCF in the coir pith matrix. Sorption capacity of coir pith (CP) before and after loading of NiHCF was investigated for cesium (Cs) in batch equilibrium studies. Kinetic studies showed that the sorption process was rapid and saturation was attained within 30 min. The applicability of non linear Langmuir, Freundlich and Redlich Peterson isotherms was examined for the experimental data. The present studies revealed that there was nearly 100% increase in the sorption capacity of CP after its surface modification with NiHCF. Owing to its low cost, fast sorption kinetics and high uptake capacity, coir pith loaded with NiHCF (CP-NiHCF) seems to be one of the most promising biosorbents for recovery of cesium from liquid nuclear wastes.     

Life cycle assessment of vertical and horizontal flow constructed wetlands for wastewater treatment considering nitrogen and carbon greenhouse gas emissions

Life cycle assessment (LCA) is used to compare the environmental impacts of vertical flow constructed wetlands (VFCW) and horizontal flow constructed wetlands (HFCW). The LCAs include greenhouse gas (N₂O, CO₂ and CH₄) emissions. Baseline constructed wetland designs are compared to different treatment performance scenarios and to conventional wastewater treatment at the materials acquisition, assembly and operation life stages. The LCAs suggest that constructed wetlands have less environmental impact, in terms of resource consumption and greenhouse gas emissions. The VFCW is a less impactful configuration for removing total nitrogen from domestic wastewater. Both wetland designs have negligible impacts on respiratory organics, radiation and ozone. Gaseous emissions, often not included in wastewater LCAs because of lack of data or lack of agreement on impacts, have the largest impact on climate change. Nitrous oxide accounts for the increase in impact on respiratory inorganic, and the combined acidification/eutrophication category. The LCAs were used to assess the importance of nitrogen removal and recycling, and the potential for optimizing nitrogen removal in constructed wetlands.     

The use of isotopic and lipid analysis techniques linking toluene degradation to specific microorganisms: applications and limitations

Phospholipid fatty acid (PLFA) analysis combined with (13)C-labeled tracers has been used recently as an environmental forensics tool to demonstrate microbial degradation of pollutants. This study investigated the effectiveness and limitations of this approach, applied to the biodegradation of toluene by five reference strains that express different aerobic toluene degradation pathways: Pseudomonas putida mt-2, P. putida F1, Burkholderia cepacia G4, B. pickettii PKO1, and P. mendocina KR1. The five strains were grown on mineral salts base medium amended with either 10 mM natural or [(13)C-ring]-labeled toluene. PLFA analysis showed that all five strains incorporated the toluene carbon into membrane fatty acids, as demonstrated by increases in the mass of fatty acids and their mass-spectrometry fragments for cells grown on (13)C-labeled toluene. Because of its ubiquitous presence and high abundance in bacteria, C16:0 fatty acid might be a useful biomarker for tracking contaminant degradation and (13)C flow. On the other hand, the (13)C-label (which was supplied at relatively high concentrations) generally exerted an inhibitory effect on fatty acid biosynthesis. Differences in fatty acid concentrations between cells grown on natural versus (13)C-labeled toluene would affect the interpretation of lipid profiles for microbial community analysis as indicated by principal component analysis of fatty acids. Therefore, caution should be exercised in linking lipid data with microbial population shifts in biodegradation experiments with (13)C-labeled tracers.