Forensic Applications of Nitrogen and Oxygen Isotopes in Tracing Nitrate Sources in Urban Environments

Ground and surface waters in urban areas are susceptible to nitrate contamination from septic systems, leaking sewer lines, and fertilizer applications. Source identification is a primary step toward a successful remediation plan in affected areas. In this respect, nitrogen and oxygen isotope ratios of nitrate, in conjunction with hydrologic data and water chemistry, have proven valuable in urban studies from Austin, Texas, and Tacoma, Washington.In Austin, stream water was sampled during stremflow and baseflow conditions to assess surface and subsurface sources of nitrate, respectively. In Tacoma, well waters were sampled in adjacent sewered and un-sewered areas to determine if locally high nitrate concentrations were caused by septic systems in the un-sewered areas. In both studies, sewage was identified as a nitrate source and mixing between sewage and other sources of nitrate was apparent. In addition to source identification, combined nitrogen and oxygen isotopes were important in determining the significance of denitrification, which can complicate source assessment by reducing nitrate concentrations and increasing δ¹⁵N values. The two studies illustrate the value of nitrogen and oxygen isotopes of nitrate for forensic applications in urban areas.     

Contribution of nitrogen sources to streams in mixed-use watershed varies seasonally in a temperate region

The Beiyun river flows through a hot spot region of Beijing-Tianjin-Hebei in China that serves a majority of occupants. However, the region experiences severe nitrate pollution, posing a threat to human health due to inadequate self-purification capacity. In that context, there is an urgent need to assess nitrate levels in this region. Herein, we used δ¹⁵N-NO₃, δ¹⁸O-NO₃ isotopes analysis, and stable isotope analysis model to evaluate the nitrate source apportionment in the Beiyun river. A meta-analysis was then used to compare the potential similarity of nitrate sources among the Beiyun riverine watershed and other watersheds. Results of nitrate source apportionment revealed that nitrate originated from the manure and sewage (contribution rate: 89.6%), soil nitrogen (5.9%), and nitrogen fertilizer (3.9%) in the wet season. While in the dry season, nitrate mainly originated from manure and sewage (91.6%). Furthermore, different land-use types exhibited distinct nitrate compositions. Nitrate in urban and suburban areas mostly was traced from manure and sewage (90.5% and 78.8%, respectively). Notably, the different nitrate contribution in the rural-urban fringe and plant-covered areas were manure and sewage (44.3% and 32.8%), soil nitrogen (26.9% and 35.7%), nitrogen fertilizer (23.5% and 29.4%), and atmospheric deposition (5.3% and 2.0%). Through a meta-analysis, we found nitrogen fertilizer, soil nitrogen, and manure and sewage as the main nitrate sources in the Beiyun riverine watershed or the other similar complexed watersheds in the temperate regions. Thus, this study provides a scientific basis for nitrate source apportionment and nitrate pollution preventive management in watersheds with complexed land-use types in temperate regions.

     

Quantifying nitrate sources in a large reservoir for drinking water by using stable isotopes and a Bayesian isotope mixing model

Drinking water reservoirs are threatened globally by anthropogenic nitrogen pollution. Hydrochemistry and isotopes were analyzed to identify spatial and temporal varieties of main nitrate sources in a large drinking water reservoir in East China. The results showed that NO₃^? was the main nitrogen form in both the dry and wet seasons, but dissolved organic nitrogen (DON) was increased in the wet season. The δ¹⁵N-NO₃^? values (+?1.3‰ to +?11.8‰) and δ¹⁸O-NO₃^? values (+?2.5‰ to +?13.5‰), combined with principal component analysis (PCA), indicated that chemical fertilizer was the main nitrate source during the dry season, while chemical fertilizer, soil N, and sewage/manure were the main nitrate sources during the wet season in the Qiandao Lake area. And, the nitrate isotopes showed the significant nitrification and assimilation in the Qiandao Lake area. A Bayesian isotopic mixing model (Stable Isotope Analysis in R) was applied to the spatial and seasonal trends in the proportional contribution of four NO₃^? sources (chemical fertilizer (CF), soil nitrogen (SN), sewage and manure (SM), and atmospheric deposition (AD)) in the Qiandao Lake area. It was revealed that CF was the most important nitrate source in the dry season, accounting for 53.4% with 19.2% of SM and 18.9% of SN, while the contribution of SN increased in the wet season, accounting for 31.6%, followed by CF (30.8%) and then SM (24.2%). The main nitrate sources in the urban area, rural area, and central lake area were CF and SN, accounting for 66.1% in the urban area, 71.7% in the rural area, and 68.2% in the central lake area. Measures should be made to improve chemical fertilizer use efficiency and to reduce nitrogen loss in the Qiandao Lake area.

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Trends in nitrate concentrations and determination of its origin using stable isotopes (18O and 15N) in groundwater of the Western Central Valley, Costa Rica

A study was conducted to evaluate long-term trends in nitrate concentrations and to try to identify the origin of nitrate using stable isotopes (15N(NO3-) and 18O(NO3-)) in the aquifers of the western Central Valley, Costa Rica, where more than 1 million people depend on groundwater to satisfy their daily needs. Data from 20 sites periodically sampled for 4 to 17 years indicate an increasing trend in nitrate concentrations at five sites, which in a period ranging from 10 to 40 years, will exceed recommended maximum concentrations. Results of isotopic analysis indicate a correspondence between land use patterns and the isotopic signature of nitrate in groundwater and suggest that urbanization processes without adequate waste disposal systems, followed by coffee fertilization practices, are threatening water quality in the region. We conclude that groundwater management in this area is not sustainable, and that land use substitution processes from agricultural activity to residential occupation that do not have proper sewage disposal systems may cause a significant increment in the nitrate contaminant load.     

Isotopes as tracers in a contaminated fractured chalk aquitard

Clusters of industrial plants often generate contaminant plumes with several potential sources. Prevention of further pollution and designing suitable remedial measures require identification of the contributing source among all potential ones and the sorting of currently active sources from historical ones. In the study area, an industrial complex in the Negev desert, Israel, contaminants could not serve as indicators for the contamination sources because of their extensive spatial distribution across the site. However, stable isotopes of oxygen, hydrogen and sulfur, as well as tritium, proved to be efficient tools for this task. The isotopic characterization of the potential end members provided the criteria for constraining a contaminating source when several alternative sources appeared viable. The isotopic fractionation of oxygen and hydrogen isotopes could be tied to the various disposal phases of the industrial wastewater. The three case studies presented here confirm the important role of isotopes as tracers in contaminated sites.     

Groundwater pollution source apportionment using principal component analysis in a multiple land-use area in southwestern China

Identification of different pollution sources in groundwater is challenging, especially in areas with diverse land uses and receiving multiple inputs. In this study, principal component analysis (PCA) was combined with geographic information system (GIS) to explore the spatial and temporal variation of groundwater quality and to identify the sources of pollution and main factors governing the quality of groundwater in a multiple land-use area in southwestern China. Groundwater samples collected from 26 wells in 2012 and 38 wells in 2018 were analyzed for 13 water quality parameters. The PCA results showed that the hydro-geochemical process was the predominant factor determining groundwater quality, followed by agricultural activities, domestic sewage discharges, and industrial sewage discharges. Agriculture expansion from 2012 to 2018 resulted in increased apportionment of agricultural pollution. In contrast, economic restructure and infrastructure improvement reduced the contributions of domestic sewage and industrial pollution. Anthropogenic activities were found the major causes of elevated nitrogen concentrations (NO₃^?, NO₂^?, NH₄⁺) in groundwater, highlighting the necessity of controlling N sources through effective fertilizer managements in agricultural areas and reducing sewage discharges in urban areas. The applications of GIS and PCA successfully identified the sources of pollutants and major factors driving the variations of groundwater quality in tested years.

     

Evaluation of surface runoff and road dust as sources of nitrogen using nitrate isotopic composition

Stable nitrogen and oxygen isotope ratios of nitrate (δ¹⁵N-NO₃ and δ¹⁸O-NO₃) have recently been used to identify nitrogen sources in water environments. However, there have been no investigations designed to determine nitrate isotopes in non-point sources in urban areas for evaluating the impact of surface deposits on nitrogen in surface runoff. In this study, we collected rainwater, surface runoff and surface deposits (road dust, roof dust and soil) to evaluate the nitrogen sources in surface runoff using nitrate isotopes. There were no large differences in δ¹⁵N-NO₃ among rainwater (−0.3‰ to 1.5‰), surface runoff (−2.7‰ to 0.4‰), leachates from road dust (−5.8‰ to 6.2‰) and soil (−11.5‰ to 0.6‰). In contrast, the δ¹⁸O-NO₃ in surface runoff (28.5-47.9‰) was lower than that in rainwater (62.7-78.6‰), and higher than that in leachates from road dust (6.1-27.6‰) and soil (−1.1‰ to 6.6‰). δ¹⁸O-NO₃ is a useful indicator for evaluating the NO₃-N sources in surface runoff. Using this indicator, NO₃-N from road dust was estimated to account for more than half of the NO₃-N in surface runoff. This is consistent with a result based on a comparison of their loads per unit surface between rainwater and surface runoff, which also showed that most of the nitrogen in surface runoff was derived from surface deposits.     

Sources of acidity in lakes and streams of the United States

Acidic (acid neutralizing capacity [ANC] < or = 0) surface waters in the United States sampled in the National Surface Water Survey (NSWS) were classified into three groups according to their probable sources of acidity: (1) organic-dominated waters (organic anions > SO4*; (2) watershed sulphate-dominated waters (watershed sulphate sources > deposition sulphate sources); and (3) deposition-dominated waters (anion chemistry dominated by inputs of sulphate and nitrate derived from deposition). The classification approach is highly robust; therefore, it is a useful tool in segregating surface waters into chemical categories. An estimated 75% (881) of acidic lakes and 47% (2190) of acidic streams are dominated by acid anions from deposition and are probably acidic due to acidic deposition. In about a quarter of the acidic lakes and streams, organic acids were the dominant source of acidity. In the remaining 26% of the acidic streams, watershed sources of sulphate, mainly from acid mine drainage, were the dominant source of acidity.     

Back-trajectory analysis and source-receptor relationships: particulate matter and nitrogen isotopic composition in rainwater

The southeastern portion of North Carolina features a dense crop and animal agricultural region; previous research suggests that this agricultural presence emits a significant portion of the state's nitrogen (i.e., oxides of nitrogen and ammonia) emissions. These findings indicate that transporting air over this region can affect nitrogen concentrations in precipitation at sites as far as 50 mi away. The study combined nitrate nitrogen isotope data with back-trajectory analysis to examine the relationship between regional nitrogen emission estimates independent of pollutant concentration information. In 2004, the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model was used to determine potential sources of nitrogen in rainwater collected at an urban receptor site in Raleigh, NC. The delta 15N isotope ratio signatures of each sample were used to further differentiate between sources of the rainwater nitrate. This study examined the importance of pollution sources, including animal agricultural activity, and meteorology on rainfall chemistry as well as the implications in fine particulate matter (PM2.5) formation. Samples that transited the dense crop and animal (swine) agricultural region of east-southeastern North Carolina (i.e., the source region) had lower delta 15N isotope ratios in the nitrate ion (average = -2.1 +/- 1.7 per thousand) than those from a counterpart nonagricultural region (average = 0.1 +/- 3 per thousand.) An increase in PM2.5 concentrations in the urban receptor site (yearly average = 15.1 +/- 5.8 microg/m3) was also found to correspond to air transport over the dense agricultural region relative to air that was not subjected to such transport (yearly average = 11.7 +/- 5.8 microg/m3).     

Numerical simulation of a fine-grained denitrification layer for removing septic system nitrate from shallow groundwater

One of the most common methods to dispose of domestic wastewater involves the release of septic effluent from drains located in the unsaturated zone. Nitrogen from such systems is currently of concern because of nitrate contamination of drinking water supplies and eutrophication of coastal waters. It has been proposed that adding labile carbon sources to septic distribution fields could enhance heterotrophic denitrification and thus reduce nitrate concentrations in shallow groundwater. In this study, a numerical model which solves for variably saturated flow and reactive transport of multiple species is employed to investigate the performance of a drain field design that incorporates a fine-grained denitrification layer. The hydrogeological scenario simulated is an unconfined sand aquifer. The model results suggest that the denitrification layer, supplemented with labile organic carbon, may be an effective means to eliminate nitrogen loading to shallow groundwater. It is also shown that in noncalcareous aquifers, the denitrification reaction may provide sufficient buffering capacity to maintain near neutral pH conditions beneath and down gradient of the drain field. Leaching of excess dissolved organic carbon (DOC) from the denitrification layer is problematic, and causes an anaerobic plume to develop in simulations where the water table is less than 5-6 m below ground surface; this anaerobic plume may lead to other down gradient changes in groundwater quality. A drain field and denitrification layer of smaller dimensions is shown to be just as effective for reducing nitrate, but has the benefit of reducing the excess DOC leached from the layer. This configuration will minimize the impact of wastewater disposal in areas where the water table is as shallow as 3.5 m.     

Modeling air quality during the California Regional PM10/PM2.5 Air Quality Study (CPRAQS) using the UCD/CIT source-oriented air quality model – Part III. Regional source apportionment of secondary and total airborne particulate matter

A comprehensive air quality modeling project was carried out to simulate regional source contributions to secondary and total (=primary + secondary) airborne particle concentrations in California's Central Valley. A three-week stagnation episode lasting from December 15, 2000 to January 7, 2001, was chosen for study using the air quality and meteorological data collected during the California Regional PM₁₀/PM_2.5 Air Quality Study (CRPAQS). The UCD/CIT mechanistic air quality model was used with explicit decomposition of the gas phase reaction chemistry to track source contributions to secondary PM. Inert artificial tracers were used with an internal mixture representation to track source contributions to primary PM. Both primary and secondary source apportionment calculations were performed for 15 size fractions ranging from 0.01 to 10 μm particle diameters. Primary and secondary source contributions were resolved for fugitive dust, road dust, diesel engines, catalyst equipped gasoline engines, non-catalyst equipped gasoline engines, wood burning, food cooking, high sulfur fuel combustion, and other anthropogenic sources.Diesel engines were identified as the largest source of secondary nitrate in central California during the study episode, accounting for approximately 40% of the total PM_2.5 nitrate. Catalyst equipped gasoline engines were also significant, contributing approximately 20% of the total secondary PM_2.5 nitrate. Agricultural sources were the dominant source of secondary ammonium ion. Sharp gradients of PM concentrations were predicted around major urban areas. The relative source contributions to PM_2.5 from each source category in urban areas differ from those in rural areas, due to the dominance of primary OC in urban locations and secondary nitrate in the rural areas. The source contributions to ultra-fine particle mass PM_0.1 also show clear urban/rural differences. Wood smoke was found to be the major source of PM_0.1 in urban areas while motor vehicle sources were the major contributor of PM_0.1 in rural areas, reflecting the influence from two major highways that transect the Valley.     

Nitrate in groundwater: an isotopic multi-tracer approach

In spite of increasing efforts to reduce nitrogen inputs into groundwater from intensive agriculture, nitrate (NO3) remains one of the major pollutants of drinking-water resources worldwide. Determining the source(s) of NO3 contamination in groundwater is an important first step for improving groundwater quality by emission control, and it is with this aim that we investigated the viability of an isotopic multi-tracer approach (delta15N, delta11B, 87Sr/86Sr), in addition to conventional hydrogeologic analysis, in two small catchments of the Arguenon watershed (Brittany, France). The main anthropogenic sources (fertilizer, sewage effluent, and hog, cattle and poultry manure) were first characterized by their specific B, N and Sr isotope signatures, and compared to those observed in the ground- and surface waters. Chemical and isotopic evidence shows that both denitrification and mixing within the watershed have the effect of buffering NO3 contamination in the groundwater. Coupled delta11B, delta15N and 87Sr/86Sr results indicate that a large part of the NO3 contamination in the Arguenon watershed originates from the spreading of animal manure, with hog manure being a major contributor. Point sources, such as sewage effluents, contribute to the NO3 budget of the two watersheds.     

Effects of land use and land cover, stream discharge, and interannual climate on the magnitude and timing of nitrogen, phosphorus, and organic carbon concentrations in three coastal plain watersheds.

In-stream nitrogen, phosphorus, organic carbon, and suspended sediment concentrations were measured in 18 subbasins over 2 annual cycles to assess how land use and land cover (LULC) and stream discharge regulate water quality variables. The LULC was a primary driver of in-stream constituent concentrations and nutrient speciation owing to differences in dominant sources and input pathways associated with agricultural, urban, and forested land uses. Stream discharge was shown to be a major factor that dictated not only the magnitude of constituent concentrations, but also the chemical form. In high discharge agricultural subbasins, where nitrate was the dominant nitrogen form, there was a negative correlation between discharge and nitrate concentration indicating groundwater inputs as the dominant pathway. In urban settings, however, nitrate was positively correlated with discharge, and, in forested subwatersheds, where dissolved organic nitrogen (DON) was the dominant nitrogen form, there was a positive correlation between discharge and DON, indicating washoff from the watershed as the dominant input pathway. Similarly, phosphorus concentrations were strongly regulated by LULC, discharge, and seasonality. This comparative study highlights that different mechanisms regulate different forms of nitrogen, phosphorus, and carbon, and thus field programs or water quality models used for regulatory purposes must assess these nutrient forms to accurately apply management plans for nutrient reductions.     

Nonpoint sources of volatile organic compounds in urban areas-relative importance of land surfaces and air

Volatile organic compounds (VOCs) commonly detected in urban waters across the United States include gasoline-related compounds (e.g. toluene, xylene) and chlorinated compounds (e.g. chloroform, tetrachloroethane [PCE], trichloroethene [TCE]). Statistical analysis of observational data and results of modeling the partitioning of VOCs between air and water suggest that urban land surfaces are the primary nonpoint source of most VOCs. Urban air is a secondary nonpoint source, but could be an important source of the gasoline oxygenate methyl-tert butyl ether (MTBE). Surface waters in urban areas would most effectively be protected by controlling land-surface sources.     

Revealing source signatures in ambient BTEX concentrations

Management of ambient concentrations of Volatile Organic Compounds (VOCs) is essential for maintaining low ozone levels in urban areas where its formation is under a VOC-limited regime. The significant decrease in traffic-induced VOC emissions in many developed countries resulted in relatively comparable shares of traffic and non-traffic VOC emissions in urban airsheds. A key step for urban air quality management is allocating ambient VOC concentrations to their pertinent sources. This study presents an approach that can aid in identifying sources that contribute to observed BTEX concentrations in areas characterized by low BTEX concentrations, where traditional source apportionment techniques are not useful. Analysis of seasonal and diurnal variations of ambient BTEX concentrations from two monitoring stations located in distinct areas reveal the possibility to identify source categories. Specifically, the varying oxidation rates of airborne BTEX compounds are used to allocate contributions of traffic emissions and evaporative sources to observed BTEX concentrations.     

Emission factors and sources of ethylene-diaminetetraacetic acid in waste water--a case study

Ethylene-diaminetetraacetic acid (EDTA) is a complexing agent and has the ability to form stable water-soluble complexes with metal ions. It is used in a variety of industrial applications including pulp and paper, metal, textile, leather rubber, pharmaceuticals, food, polymer production and others. Most of these applications are water based and lead to emissions into the waste water and reach sewage treatment plants. Industrial sources and municipal waste waters were monitored simultaneously. Mixed samples were taken over periods of one week at nine sample sites. The concentrations of EDTA were measured in waste water samples by gas chromatography using N-selective detection. The results showed that, although, the concentrations and loads were variable the paper manufacturing industry was the major EDTA contributor to the influent of the waste water treatment plant and contributed more than 98% of the total load. All the other sources including two household areas, were comparably low. In waste water of households concentrations between 10 and 70 microg/l EDTA could be detected. Concentrations of EDTA from different industrial waste water sources ranged from 28 up to 3980 microg/l. Influent and effluent concentrations of the WWTP were usually high in the range of 500-940 and 390-760 microg/l; respectively. Elimination rates averaged 15%, the calculation is based on emission loads. Specific emission factors were calculated based on population equivalents.     

盐河淮阴段氨氮污染变化分析

在分析盐河淮阴段氨氮污染的特征后，对氨氮的来源进行了研究。结果表明，畜牧业和农业面源都是比较显著的氨氮污染源，但未经集中式污水处理厂处理的生活污水，则成为盐河淮阴段最重要的氨氮污染源。     

Surface water acidification in the South Pennines I. Current status and spatial variability

The South Pennines, an area of acid-sensitive geology at the centre of a major industrial region, have undergone perhaps the most severe historic exposure to sulphur and nitrogen deposition in the UK. This study addresses a lack of existing research on the region by presenting the findings of a survey of 62 surface waters sampled during a 1-week period in April 1998. Results indicate that acidification in the region is acute; 27 of the sampled surface waters had a negative acid neutralising capacity (ANC) and 28 had a pH below 5.0. Minimum recorded pH values were below 4.0. Non-marine sulphate levels were extremely high (median 222 microeq/1), and widespread high nitrate concentrations (median 41 microeq/1) suggest that soils in the region as a whole may be at an advanced stage of nitrogen saturation. A consistent relationship was identified between site acidity and the balance between the major weathering-derived cations, calcium and magnesium, and sulphate. This could in turn be linked to catchment soil type and land use, with the most acidic conditions occurring in peat-dominated catchments, where weathering is minimal and the influence of atmospheric deposition most pronounced. Percentage of peat in each catchment was the single best predictor of surface water acidity. Nitrate concentrations, although not a dominant control on acidity, varied significantly according to land use. Elevated concentrations were observed in catchments containing forestry, due to enhanced deposition inputs, and in catchments containing improved land, linked to fertiliser use. Ammonium concentrations, although low at most catchments, were a significant component of the inorganic nitrogen total in a number of surface waters draining waterlogged peat catchments.     

Gaseous Pollutants in St. Louis and Other Cities

During the fall of 1972, a study was undertaken to characterize gaseous air pollutants in the St. Louis metropolitan area. Information obtained in this study will be used in planning air pollution modeling studies to be carried out over the next 4 or 5 years under the Regional Air Pollution Study (RAPS) of the Environmental Protection Agency. From analyses of roadway samples, it was found that certain compounds in automotive emissions such as acetylene, carbon monoxide, o-xylene, ethylene, and 2-methylpentane occur in consistent proportions to other compounds. The concentrations of these indicator compounds in atmospheric samples were used to estimate the amounts of other hydrocarbons present that are attributable to automotive related emissions. Methane, ethane, and propane were found to originate principally from nonautomotive sources, both at St. Louis University and the St. Louis CAMP station. Similar concentrations were found in urban and non-urban areas. A comparison of ethylene-CO and propyl-ene-CO ratios in urban and non-urban areas indicates that CO can serve as an indicator of transport of urban pollutants. Sunlight irradiations of captured air samples showed increasing ozone production with increasing initial concentrations of hydrocarbons and nitrogen oxides. Substantial ozone and peroxyacetyl nitrate were formed from a total non-methane hydrocarbon concentration of only ¹/₄ ppm C.     

Loading estimates of lead, copper, cadmium, and zinc in urban runoff from specific sources

Urban stormwater runoff is being recognized as a substantial source of pollutants to receiving waters. A number of investigators have found significant levels of metals in runoff from urban areas, especially in highway runoff. As an initiatory study, this work estimates lead, copper, cadmium, and zinc loadings from various sources in a developed area utilizing information available in the literature, in conjunction with controlled experimental and sampling investigations. Specific sources examined include building siding and roofs; automobile brakes, tires, and oil leakage; and wet and dry atmospheric deposition. Important sources identified are building siding for all four metals, vehicle brake emissions for copper and tire wear for zinc. Atmospheric deposition is an important source for cadmium, copper, and lead. Loadings and source distributions depend on building and automobile density assumptions and the type of materials present in the area examined. Identified important sources are targeted for future comprehensive mechanistic studies. Improved information on the metal release and distributions from the specific sources, along with detailed characterization of watershed areas will allow refinements in the predictions.