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Article

Potential Sources of Ammonium-Nitrogen in the Coastal Groundwater Determined from a Combined Analysis of Nitrogen Isotope, Biological and Geological Parameters, and Land Use

1
Graduate School of Integrated Arts and Sciences, Hiroshima University, Higashihiroshima 7398521, Japan
2
Graduate School of Advanced Science and Engineering, Hiroshima University, Higashihiroshima 7398521, Japan
3
Graduate School of Environmental and Life Science, Okayama University, Okamaya 7008530, Japan
4
Research Center for Geotechnology, Indonesian Institute of Sciences, Bandung 40135, Indonesia
*
Author to whom correspondence should be addressed.
Water 2021, 13(1), 25; https://doi.org/10.3390/w13010025
Submission received: 25 November 2020 / Revised: 16 December 2020 / Accepted: 22 December 2020 / Published: 25 December 2020
(This article belongs to the Section Hydrology)

Abstract

:
The origin of ammonium-nitrogen in Indonesian coastal groundwater has not been intensively examined, meanwhile the elevated concentration remains a concern. This research aims at tracing the potential sources of ammonium-nitrogen in the groundwater of Indramayu, Indonesia where groundwater is vital for livelihood. From results, a combined examination of nitrogen isotope, coliform bacteria, land-use, and geology confirmed the natural and anthropogenic origins of ammonium-nitrogen in the groundwater. In the brackish-water aquaculture region, groundwater has δ15NNH4 values from +1.8 to +4.8‰ signifying that ammonium-nitrogen is derived from mineralization of organic nitrogen to ammonium. Furthermore, ammonium has a significantly positive relationship with sodium indicating the exchangeable ammonium is mobilized to groundwater via cation exchange. Meanwhile ammonium-nitrogen from anthropogenic waste was detected in agricultural and residential region. The groundwater has more varied δ15NNH4 values, from −2.9 to +16.1‰, which implies attenuation of ammonium-nitrogen from several sources namely manure, mineral fertilizer, sewage, and pit latrines. Also, the presence of E. coli confirms the indication of human and animal waste contamination. However, since ammonium has no relationship with sodium, cation exchange is not feasible and ammonium-nitrogen flows into the groundwater from anthropogenic sources along with liquid wastes.

Graphical Abstract

1. Introduction

Groundwater as one of the clean water sources is presently experiencing nitrogen contamination because of human activities [1,2,3]. Ammonium is one form of dissolved inorganic nitrogen that is naturally occurring in low concentrations within groundwater. Generally, under aerobic condition, ammonium-nitrogen (NH4+–N) concentration in groundwater is <0.2 mg/L, and it may increase more than ten times under anaerobic environment [4]. The considerably high ammonium groundwater concentrations are indications of anthropogenic contamination from sources such as fertilizer, manure, septic tanks, and sewage [4,5,6]; therefore, these undesirable concentrations need to be removed [7,8]. Additionally, previous research found that high concentration of ammonium in groundwater is significantly correlated with high contents of more dangerous contaminants, which are dissolved iron and manganese [9].
Several studies in Indonesian coastal alluvial region have reported the groundwater quality issues with emphasis laid on metals and nitrate contaminations [10,11,12]. Equally, NH4+–N was also detected in shallow and deep groundwater with concentrations approximately 7.8 and 12 mg/L, respectively [13]. However, the evaluation of the ammonium source in this study was limited, which was mainly derived from nitrate denitrification. An in-depth study to trace other potential sources of ammonium in Indonesia is yet to be investigated. Additionally, Indonesian coastal groundwater is also vulnerable to salinization [14]. At the same time, salinization itself is known to have a positive relationship with the elevated concentrations of other contaminants, including ammonium [9,15,16,17].
Many methods have been devised to understand the origin of ammonium-nitrogen. Among them, nitrogen isotope (δ15N) is one of the most reliable and widely used ammonium tracer [6,18,19]. However, some issues need to be overcome for interpreting the δ15N value. For example, the different sources of ammonium may have similar δ15N signatures, and fractionation may occur during ammonium transport from the subsurface to the groundwater [20]. Consequently, multi-tracer parameters are required to eliminate these problems [20]. Land-use evaluation can help to identify contamination sources. This type of evaluation has been successfully used to appraise nitrate groundwater contamination [21]. The combination of nitrogen isotope and land-use to trace ammonium source can still be enhanced by analyzing the geological settling and bacterial content in the water. Previous findings revealed that soils and sediments are related to elevated concentrations of ammonium in groundwater [6,22]. On the other hand, coliform and E. coli parameters are useful tracers to confirm human waste contamination which is also a potential source of ammonium contamination [4]. In this research, we trace the potential sources of ammonium in coastal alluvial groundwater using the following combined tracers; nitrogen isotope (δ15N), bacterial coliform analysis (total coliform and E. coli), land use, and geological features. In addition, the effect of saline water on ammonium was evaluated with respect to major cations contents. Finally, from the combined tracing parameters, we expect to find the anthropogenic and salinization impact on NH4+–N contents in groundwater.

2. Study Site

This study was conducted in the coastal alluvial aquifer of Indramayu, located in the northern part of West Java Island, Indonesia (107°52′–108°36′ E and 6°15′–6°40′ W). Indramayu is vital as a rice- and fish-production area with increasing gross domestic regional product (GRDP) particularly in the farming and fishery sector [23]. Groundwater is essential to support livelihood activities in this region because only less than 60% of the population can access the potable water provided by the government [23]. However, comprehensive information on the groundwater quality is limited. Hence, understanding groundwater ammonium sources in this area is valuable to provide a strong scientific base for the sustainable management of groundwater.

2.1. Land Uses of Indramayu

Indramayu is a lowland area with a total area greater than 240,000 ha. The main land-use categories are agriculture, brackish-water aquaculture, and residential (Figure 1a). Agricultural land that mainly consists of paddy fields is the primary land-use category, covering over 70% of the total area. The second-largest land-use category is brackish-water aquaculture, accounting for about 13% of the land use—aquaculture is mainly adopted in the northernmost part. The last major land-use category is the settlement that covers less than 11% and is mostly located along Cimanuk River. From 2002 to 2017, the agricultural and settlement areas slightly expanded, while the area under brackish-water aquaculture decreased. Since then, there was no significant change in the three main land-use categories (Figure 1b).
During the field campaigns, we observed that agricultural areas and settlements are not strictly defined, this is explained by the fact that the agricultural area is extensive and surrounds the entire residential area. The collection of groundwater samples from agriculture and settlement areas were from houses that have dug or bore wells. Groundwater in agriculture and settlement areas were expected to have similar characteristics because of their undefined boundaries. On the other hand, the boundary between the brackish-water aquaculture and agriculture was quite clear. The groundwater samples from brackish-water aquaculture were collected from bore wells which are used to fill the ponds. From the aforementioned land-uses, we classified them into two groups: lower coastal zone (LC) comprising brackish-water aquaculture area and the upper coastal zone (UC) consisting of agricultural and settlement areas (Figure 2).

2.2. Geology and Aquifer System of Indramayu

The Indramayu Coast is a delta [24,25,26] formed by sedimentary materials supplied by the Cimanuk River [27]. Based on the Geological Map of Indramayu Quadrangle in Java [28], the study area generally consists of old to young lithologies, including tuffaceous sandstone and conglomerate (Qav), flood plain deposits (Qaf), beach ridge deposits (Qbr), coastal deposits (Qac), deltaic deposits (Qad), and young river deposits (Qa) (Figure 3a). The Indramayu region is essentially composed of quaternary rocks. The oldest Pleistocene quaternary rock units in the region are tuffaceous sandstone and conglomerate (Qav), conglomeratic sandstone, tuffaceous sandstone, and tuff. Holocene sediments are deposited on the upper part. They include flood plain deposits (Qaf) in the form of sandy-humic clay, clayey sand, and partly tuff; beach ridge deposits (Qbr) in the form of coarse to fine-grained sand and clay with abundant mollusks; coastal deposits (Qac) in the form of silt, clay, sand, and fragments of mollusks; deltaic deposits (Qad) in the form of silt, brown clay, and some mollusks; and young river deposits (Qa) in the form of sand, silt, and brown clay.
The vertical geological profile from south to north shows a large aquifer reservoir interspersed with clay and silt in the area (Figure 3b). In the north, there is the thickest clay layer derived from marine deposits. According to previous studies, the groundwater here has high chloride concentrations, ranging from 1500 to 12,000 mg/L, which is categorized as brackish-salt and salt water [30].

3. Samples Collection and Analysis

3.1. Sediment Samples

Sediment analysis was performed to evaluate the general geological conditions that possibly promote the natural attenuation of NH4+–N in the groundwater. The sediments samples were collected at different depths from two boreholes in UC area (DH01) and LC area (DH05) (Figure 3a). We selected the depth based on the textures—clay, silt, and sand (Figure 3b). The analysis was conducted for ratio of exchangeable ammonium (NH4+) to total cations (NH4+, Na+, K+, Mg2+, and Ca2+), stable isotopes of nitrogen (δ15N), nitrogen content (%), and the cation exchange capacity (CEC). Method of analysis for each parameter is as follows: Composition of δ15N (‰) was determined by Thermo Finnigan DELTAplus Advantage+FLASH2000; N content (%) was measured by high temperature combustion; exchangeable NH4+ was measured by soil extraction with NH4Oac at pH 7.0 and follow by atomic absorption spectrophotometry (AAS); and CEC value was measured by summing cations that are attracted to the negative surface charges in sediments samples.
Analysis of δ15N and N content were conducted at the Chikyu Kagaku Kenkyusho (Geo-Science Laboratory, Nagoya, Japan) while ratio of exchangeable ammonium to total cations and CEC were measured at the Soil Fertility and Plant Nutrition Laboratory, University of Padjajaran, Bandung, Indonesia.

3.2. Groundwater Samples

In all, 28 groundwater samples were collected during dry season in November 2019 from LC area (n = 10) and UC area (n = 18) (Figure 2). The concentrations of NH4+–N, nitrate-nitrogen (NO3–N), and nitrite-nitrogen (NO2–N) were determined using a continuous-flow automated nutrient analyzer (SwAAt, BLTEC, Tokyo, Japan) at the Biogeochemistry Laboratory, Hiroshima University, Japan. The analysis of NH4+–N (δ15NNH4) was conducted by using a continuous-flow type stable isotope ratio mass spectrometer (DELTA plus Advantage + FLASH2000; Thermo Finnigan, San Jose, CA, USA) with a precision of ±0.2‰ at the Chikyu Kagaku Kenkyusho (Geo-Science Laboratory, Dubai, UAE), Japan. Glycine, L-Alanine, and L-Histidine were used as working standards to calibrate the isotope ratio with the international standard. Sample preparation for δ15NNH4 analysis was performed at the Laboratory of Biogeochemistry, Hiroshima University, Japan. The NH4+–N in the sample was first diffused following the procedure and materials and chemicals adopted by Koba et al. (2010) [31]. However, some adjustments were made for the analysis in this study. The incubation period here was 24 h, which is sufficient for capturing all NH4+–N from samples to the glass filter and the maximum volume of sample was 40 mL. Besides, the laboratory analysis is limited for groundwater samples with NH4+–N content greater than 20 μg. First, 10 samples and 14 samples from the LC and UC groundwater, respectively, meeting the requirements for δ15NNH4 measurement were used. Furthermore, coliform bacteria analysis (total coliform and E. coli) was completed in the health department facility in Indramayu by using the most probable number method on the same day of sample collection.
Furthermore, the contents of major cations, comprising Na+, K+, Mg2+, and Ca2+, were analyzed by ion chromatography with conductivity detection on an ICS-2100 (Thermo Fisher Scientific Inc., Waltham, MA, USA) with analytical precisions of <1% for Na+, Mg2+, and Ca2+, and <2% for K+. For dissolved organic carbon (DOC), analysis was performed using a total organic carbon analyzer (TOC-VCPH, Shimadzu, Kyoto City, Japan). The analysis of major ions and DOC were carried out at the Laboratory of Geothermal Engineering, Hirosaki University, Japan.
Samples for the nitrogen isotope and chemical analysis were first filtered with 0.2 µm polytetrafluoroethylene or DISMIC-25HP (for DOC) membranes and then placed into polyethylene bottles and glass vials (for DOC). The samples bottles were pretreated before collecting the samples: they had been soaked in 10% HCl solution for 24 h, washed, and then rinsed thrice with distilled water; further, they were rinsed thrice in the field with well water before collecting the sample. For biological analysis, samples were kept in sterilized glass bottles prepared by the health department in Indramayu, Indonesia.
The statistical analysis was carried out to find the NH4+–N relationship with DOC and major cations. The effect of DOC and major cations on NH4+–N concentrations is demonstrated by coefficient determination (R2). Furthermore, the significance of the relationship is shown by the p value with 95% confidence level.

4. Results and Discussion

4.1. Chemical Properties of Sediments

Sediments analysis results show that the ratio of exchangeable NH4+ to total cations (NH4+ and major cations) is high in both UC and LC deposits and does not vary significantly with depth (Figure 4a,b). Similarly, the δ15N value does not change considerably with sediment depth and texture in either UC or LC deposits (Figure 4c,d). The δ15N ratio of UC and LC deposits varies from +3.1 to +3.9‰ and +2.9 to +3.5‰ and, respectively. According to Evans [32], the δ15N value between 0 and +5‰ may indicate nitrogen conversion from organic matter to ammonium by mineralization. Furthermore, the nitrogen content in the first layer of clay and silt in UC deposits is relatively lower than that in LC deposits (Figure 4e,f). Therefore, the mineralization of soil nitrogen is more likely to occur in LC deposits. Subsequently, ammonium as a mineralization product is then mobilized by the cation exchange process and transported to sampling wells. This assumption is supported by the CEC value of LC deposits, which is relatively higher than UC deposits (Figure 4g,h). However, the properties of sediments can differ spatially. Therefore, the available sediment data only indicates the general condition of the study area.

4.2. Potential Sources of Ammonium-Nitrogen in Groundwater Systems

Previous findings have shown that the concentration of NH4+–N in the samples is predominant compared to NO3–N and NO2–N, particularly in the LC region [30]. NH4+–N concentrations in LC and UC groundwater from previous studies ranged from 2.3 to 9.0 mg/L and 0.04 to 7.0 mg/L, respectively. On the other hand, the NO3–N concentration was mostly <0.2 mg/L, and NO2–N content was <0.02 mg/L. Similar to a previous study, the current study also found a high content of NH4+–N (Figure 5). Only two samples from UC groundwater (DH07 and DH13) had a high concentration of NO3–N. However, this value was still below the standard drinking water threshold [4]. The NO2–N content was very low (≤0.02 mg/L). The content of NH4+–N was generally higher in LC than in UC groundwater. The concentration of NH4+–N in LC and UC groundwater varied from 2.35 to 12.97 mg/L and 0.07 to 3.19 mg/L, respectively. Significant amounts of NH4+–N compared to NO3–N or NO2–N may be an indicator of a reducing environment that can cause the dissolution of metals such as iron, manganese, and arsenic [22,33].
Nitrate may be reduced in the dissimilatory nitrate reduction to ammonium (DNRA) as a result of microbial activities facilitated by organic carbon or nitrate [33]. This process is likely to occur in the LC groundwater since DOC has a positive and significant relationship with both NO3–N and NH4+–N (Figure 6a,b, respectively). However, further investigation is required to confirm this origin.
The relationship of δ15NNH4 and NH4+–N in Figure 7 shows that δ15NNH4 in the LC groundwater has a narrow range of values, from 1.8 to 4.8‰ (Table 1), and it is relatively stable over the wide range of NH4+–N concentrations, from 2.35 to 14.6 mg/L (Table 1). Still in Figure 7, this also presents the isotopic composition of δ15NNH4 from several sources which have been discovered from previous studies [6,19]. By using these references, we propose that the ammonium in the LC groundwater is unlikely to be of human and animal waste origin; it probably is mainly derived from the mineralization of organic and inorganic nitrogen in sediment. Meanwhile, the groundwater at LC reveals the presence of coliform bacteria, but none of it originated from E. coli (Table 1). This finding indicates the absence of contamination by human and animal feces [4] which further supports the interpretation based on δ15NNH4. Additionally, the LC area has a thick clay layer (Figure 3b) with potentially high organic matter contents [34]. The organic matter is not only a natural source of ammonium, but is also a facilitator of microbial activities that, in turn, generate a reducing environment. This condition was confirmed earlier in several studies [6,22].
On the other hand, Figure 7 also shows that the δ15NNH4 values in the UC groundwater are varied, from −2.9 to 16.1‰ (Table 1), within a relatively narrow concentration range of NH4+–N, from 0.42 to 3.19 mg/L (Table 1), suggesting that ammonium is derived from diverse sources. The compositions of δ15NNH4, >5‰, suggest that ammonium-nitrate are potentially derived from animal manure and household waste [6,19]. This observation is consistent with the presence of E. coli in the samples (Table 1). Furthermore, the source of ammonium for δ15NNH4 values ≤ 5‰ may be from the application of mineral fertilizers in paddy fields area and sewage infiltration [19]. Since most of the UC groundwater samples were collected from a shallow aquifer (≤8 m), the results indicate the possibility that poor wastewater treatment and utilization of pit latrine less than 2 m from the well led to the transport of leaked wastewater into the aquifer [35,36].
The comparison of NH4+–N concentrations and δ15NNH4 compositions between LC and UC groundwater showed that the LC groundwater was potentially more vulnerable to ammonium contamination. Interestingly, the relative high ammonium-nitrogen in LC groundwater was from natural source. Previous findings in more developing Indonesian coastal area suggest that anthropogenic waste is the primary source of ammonium in groundwater [13]. The presence of ammonium in both areas shows the heterogeneity of groundwater conditions in Indonesia coastal areas.

4.3. Relationship between Ammonium-Nitrogen and Water Chemical Properties

The relatively high concentration of NH4+–N in LC groundwater is consistent with the significantly elevated concentrations of major cations, mostly Na+ (Figure 8). High cation content is typical of high salinity water [37]. The source of high salinity is possibly associated with infiltration of brackish-water from the pond or marine clay sediment. Figure 8a–d show a strong positive and significant relationship between NH4+–N and cations. Hence, exchangeable ammonium from sediments can be released into groundwater by exchanging cations, particularly Na+, as the dominant cation [15,16,38]. It is also important to consider that the lithology of LC site sediments is composed of thick clay (Figure 3b), which generally impedes exchangeable ammonium by the sorption process [16]. Therefore, more exchangeable ammonium can be deposited in sediments [16] and released into groundwater through the cation exchange process under high salinity conditions [15,38].
On the other hand, the content of major cations in UC groundwater is relatively low and has no rational relationship with NH4+–N (Figure 8). Moreover, the p-value for the relationship between NH4+– and all cations is not considerable. This implies that the transfer of ammonium from sediments to groundwater by the cation exchange mechanism is unlikely.
Figure 9 shows the average concentrations of total major cations, NH4+, and δ15NNH4, in three different classifications of groundwater depth: shallow (≤5 m), medium (≥5–20 m), and deep (≥25 m). The total content of major cations in UC groundwater is relatively low and similar at all depths, in the range of 23 to 48 meq/L (Figure 9a). LC groundwater, on the other hand, has a very high content of major cations, which implies high salinity groundwater, especially at shallow (377 meq/L) and medium (352 meq/L) depths (Figure 9b). As a compromise, UC groundwater (Figure 9c) has significantly lower ammonium ions than LC groundwater, respectively from 0.06 to 0.11 meq/L and 0.43 to 0.57 meq/L (Figure 9d). Moreover, the concentration of NH4+ in groundwater decreases as groundwater depth increases, according to the pattern of the total content of major cations relative to depth. Overall, the cations and ammonium ion contents at these two sites indicate that ammonium is likely to be mobilized because of the cation exchange at the LC site.
In addition, shallow UC groundwater has a relatively high value of δ15NNH4, ±7.6‰ on average (Figure 9e), which is typical of the δ15NNH4 ratio of household waste and animal manure [6,19]. This finding is consistent with previous assumptions about the leakage of wastewater and manure into shallow groundwater. Nevertheless, still in Figure 9e, UC groundwater at medium depths has a low δ15NNH4 value (±0.8‰ on average) in the range of ammonium from mineral fertilizers. At the same time, the δ15NNH4 value was below the detection limit in deeper UC groundwater. Finally, the δ15NNH4 ratio in LC groundwater was more uniform (±3‰ on average) (Figure 9f), suggesting that ammonium at all depths was potentially derived from the mineralization of nitrogen in sediments [6,19].

5. Conclusions

The combined parameters of δ15NNH4, coliform bacteria, land use, and geology in this research can trace well the potential sources of NH4+–N in the coastal alluvial groundwater in Indramayu, Indonesia. The origins of NH4+–N are natural and anthropogenic sources located in the lower and upper coastal areas, respectively. The mobilization of NH4+–N to the groundwater differ depending on the source. From the results, the following conclusions can be drawn:
  • NH4+–N in the lower coastal region, occupied by brackish-water aquaculture, potentially originated from the mineralization of organic nitrogen in sediments to ammonium. In agreement with this origin, the ratios of δ15N in the sediments indicate the mineralization of nitrogen. However, contamination by anthropogenic activity is possible considering the high values of total coliform bacteria. The strongly positive and significant relationship of NH4+–N and Na+ suggests that under high salinity, the exchangeable NH4+ is mobilized from sediments to the groundwater through cation exchange. Additionally, the high salinity of groundwater possibly arises from the brackish-water pond and marine clay.
  • Further, attenuation of ammonium-nitrogen from manure, sewage, and pit latrines occurs in the groundwater in the upper coastal region, where land is used mainly for agricultural and residential purposes. Both total coliform and E. coli values confirm this condition. The ratios of δ15N in several layers of sediments suggest the possibility of nitrogen mineralization to ammonium; nevertheless, the nitrogen contents suggest that this process is more likely in the sediments of lower coastal region. The significantly lower salinity followed by weak and not significant relationships of NH4+–N and all major cations indicate less possibility of NH4+–N mobilize to groundwater through cation exchange.

Author Contributions

Conceptualization, A.F.R. and S.-I.O.; formal analysis, A.F.R., M.S., M.M., F.H., K.S., and S.W.; funding acquisition, S.-I.O. and M.S.; investigation, A.F.R., S.-I.O., M.S., K.S., and S.W.; methodology, A.F.R., S.-I.O., and M.S.; project administration, S.-I.O. and M.S.; supervision, S.-I.O., M.M., and F.H.; writing—original draft, A.F.R.; writing—review and editing, A.F.R., S.-I.O., and M.S. All authors have read and agreed to the published version of the manuscript.

Funding

This material is based on work supported by: 1. The Asia-Pacific Network for Global Change Research (APN) under Grant No. CRRP2019-09 MY-Onodera (funder ID: http://dx.doi.org/10.13039/100005536). 2. All opinions, findings, conclusions, or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of APN. While the information and advice in this publication are believed to be true and accurate at the date of publication, neither the editors nor APN accept any legal responsibility for any errors or omissions that may be made. APN and its member countries make no warranty, expressed or implied, with respect to the material contained herein. 3. Japanese Society for the Promotion of Sciences Grant-in-Aid for Scientific Research B (JSPS KAKENHI B) with Grant Number 17H04494. 4. Priority Research Program of Deputy of Earth Science, the Indonesian Institute of Sciences (LIPI), entitled “Degradation of Groundwater Resources and The Potential of Land Subsidence due to Climate Changes and Anthropogenic Activities in The Coastal of Cimanuk Watershed”, which was funded by LIPI in 2016–2017 fiscal year.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data sharing not applicable.

Acknowledgments

Authors wish to thank Seiichiro Ioka from Hirosaki University and Robert M. Delinom for providing valuable discussion and highly supported analysis of some water quality parameters. Many thanks to Rizka Maria, Wahyu Purwoko, and Dady Sukmayadi from Research Center for Geotechnology Indonesian Institute of Sciences for field research support; and Kimbi Sharon Bih and Yusuke Tomozawa from Laboratory of Biogeochemistry for supporting laboratory analysis.

Conflicts of Interest

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References

  1. Hansen, B.; Thorling, L.; Schullehner, J.; Termansen, M.; Dalgaard, T. Groundwater nitrate response to sustainable nitrogen management. Sci. Rep. 2017, 7, 1–12. [Google Scholar] [CrossRef] [PubMed]
  2. Shakya, B.M.; Nakamura, T.; Kamei, T.; Shrestha, S.D.; Nishida, K. Seasonal groundwater quality status and nitrogen contamination in the shallow aquifer system of the Kathmandu Valley, Nepal. Water 2019, 11, 2184. [Google Scholar] [CrossRef] [Green Version]
  3. Zhou, Y.; Li, P.; Xue, L.; Dong, Z.; Li, D. Solute geochemistry and groundwater quality for drinking and irrigation purposes: A case study in Xinle City, North China. Geochemistry 2020, 80, 125609. [Google Scholar] [CrossRef]
  4. WHO. Guidelines for Drinking-Water Quality: Fourth Edition Incorporating the First Addendum; World Health Organization: Geneva, Switzerland, 2017. [Google Scholar]
  5. Koda, E.; Sieczka, A.; Osinski, P. Ammonium concentration and migration in groundwater in the vicinity of waste management site located in the neighborhood of protected areas of Warsaw, Poland. Sustainability 2016, 8, 1253. [Google Scholar] [CrossRef] [Green Version]
  6. Norrman, J.; Sparrenbom, C.J.; Berg, M.; Dang, D.N.; Jacks, G.; Harms-Ringdahl, P.; Pham, Q.N.; Rosqvist, H. Tracing sources of ammonium in reducing groundwater in a well field in Hanoi (Vietnam) by means of stable nitrogen isotope (δ15N) values. Appl. Geochem. 2015, 61, 248–258. [Google Scholar] [CrossRef]
  7. Li, S.; Huang, G.; Kong, X.; Yang, Y.; Liu, F.; Hou, G.; Chen, H. Ammonium removal from groundwater using a zeolite permeable reactive barrier: A pilot-scale demonstration. Water Sci. Technol. 2014, 70, 1540–1547. [Google Scholar] [CrossRef]
  8. Huang, G.; Liu, F.; Yang, Y.; Deng, W.; Li, S.; Huang, Y.; Kong, X. Removal of ammonium-nitrogen from groundwater using a fully passive permeable reactive barrier with oxygen-releasing compound and clinoptilolite. J. Environ. Manag. 2015, 154, 1–7. [Google Scholar] [CrossRef]
  9. Zhang, Z.; Xiao, C.; Adeyeye, O.; Yang, W.; Liang, X. Source and Mobilization Mechanism of Iron, Manganese and Arsenic in Groundwater of Shuangliao City, Northeast China. Water 2020, 12, 534. [Google Scholar] [CrossRef] [Green Version]
  10. Winkel, L.; Berg, M.; Amini, M.; Hug, S.J.; Johnson, C.A. Predicting groundwater arsenic contamination in Southeast Asia from surface parameters. Nat. Geosci. 2008, 1, 536–542. [Google Scholar] [CrossRef] [Green Version]
  11. Onodera, S.I. Subsurface pollution in Asian megacities. In Groundwater and Subsurface Environments; Taniguchi, M., Ed.; Springer: Tokyo, Japan, 2011; pp. 159–184. [Google Scholar] [CrossRef]
  12. Hosono, T.; Nakano, T.; Shimizu, Y.; Onodera, S.I.; Taniguchi, M. Hydrogeological constraint on nitrate and arsenic contamination in Asian metropolitan groundwater. Hydrol. Processes 2011, 25, 2742–2754. [Google Scholar] [CrossRef]
  13. Umezawa, Y.; Hosono, T.; Onodera, S.I.; Siringan, F.; Buapeng, S.; Delinom, R.; Yoshimizu, C.; Tayasu, I.; Nagata, T.; Taniguchi, M. Tracing the sources of nitrate and ammonium contaminations in groundwater at developing Asian megacities, using GIS data and nitrate δ15N and d18O. Sci. Total Environ. 2008, 404, 361–376. [Google Scholar] [CrossRef] [PubMed]
  14. Kagabu, M.; Shimada, J.; Delinom, R.; Tsujimura, M.; Taniguchi, M. Groundwater flow system under a rapidly urbanizing coastal city as determined by hydrogeochemistry. J. Asian Earth Sci. 2011, 40, 226–239. [Google Scholar] [CrossRef] [Green Version]
  15. Jiao, J.J.; Wang, Y.; Cherry, J.A.; Wang, X.; Zhi, B.; Du, H.; Wen, D. Abnormally high ammonium of natural origin in a coastal aquifer-aquitard system in the Pearl River Delta, China. Environ. Sci. Technol. 2010, 44, 7470–7475. [Google Scholar] [CrossRef] [PubMed]
  16. Buss, S.R.; Herbert, A.W.; Morgan, P.; Thornton, S.F.; Smith, J.W.N. A Review of Ammonium Attenuation in Soil and Groundwater. Q. J. Eng. Geol. Hydrogeol. 2004, 37, 347–359. [Google Scholar] [CrossRef]
  17. Wen, X.; Lu, J.; Wu, J.; Lin, Y.; Luo, Y. Influence of coastal groundwater salinization on the distribution and risks of heavy metals. Sci. Total Environ. 2019, 652, 267–277. [Google Scholar] [CrossRef]
  18. Lingle, D.A.; Kehew, A.E.; Krishnamurthy, R.V. Use of nitrogen isotopes and other geochemical tools to evaluate the source of ammonium in a confined glacial drift aquifer, Ottawa County, Michigan, USA. Appl. Geochem. 2017, 78, 334–342. [Google Scholar] [CrossRef]
  19. Nikolenko, O.; Jurado, A.; Borges, A.V.; Knӧller, K.; Brouyѐre, S. Isotopic composition of nitrogen species in groundwater under agricultural areas: A review. Sci. Total Environ. 2018, 621, 1415–1432. [Google Scholar] [CrossRef]
  20. Kendall, C.; Elliott, E.M.; Wankel, S.D. Tracing anthropogenic inputs of nitrogen to ecosystems. In Stable Isotopes in Ecology and Environmental Science, 2nd ed.; Michener, R.H., Lajtha, K., Eds.; Blackwell Publishing: Oxford, UK, 2007; pp. 375–449. [Google Scholar] [CrossRef]
  21. Matiatos, I. Nitrate source identification in groundwater of multiple land-use areas by combining isotopes and multivariate statistical analysis: A case study of Asopos basin (Central Greece). Sci. Total Environ. 2016, 541, 802–814. [Google Scholar] [CrossRef]
  22. Berg, M.; Trang, P.T.; Stengel, C.; Buschmann, J.; Viet, P.H.; Van Dan, N.; Giger, W.; Stüben, D. Hydrological and sedimentary controls leading to arsenic contamination of groundwater in the Hanoi area, Vietnam: The impact of iron-arsenic ratios, peat, riverbank deposits, and excessive groundwater abstraction. Chem. Geol. 2008, 249, 91–112. [Google Scholar] [CrossRef] [Green Version]
  23. Statistic of Indramayu Regency. Indramayu Regency in Figures; BPS: Indramayu, Indonesia, 2019; 300p. (In Indonesian) [Google Scholar]
  24. Tjia, H.D.; Asikin, S.; Atmadja, R.S. Coastal accretion in western Indonesia. Bull. Natl. Inst. Geol. Min. Bdg. 1968, 1, 15–45. [Google Scholar]
  25. Hehannusa, P.E.; Hadiwisastra, S.; Djuhanah, S. Sedimentation of new Delta Cimanuk Sedimentasi Delta Baru Cimanuk. Geol. Indones. 1975, 3, 12–35. (In Indonesian) [Google Scholar]
  26. Kloosterman, F.H. Groundwater Flow Systems in the Northern Coastal Lowlands of West-and Central Java, Indonesia. Ph.D. Thesis, Vrije Universiteit, Amsterdam, The Netherlands, 1989. [Google Scholar]
  27. Yuanita, N.; Tingsanchali, T. Development of a river delta: A case study of Cimanuk river mouth, Indonesia. Hydrol. Process 2008, 22, 3785–3801. [Google Scholar] [CrossRef]
  28. Achdan, A.; Sudana, D. Geological Map of the Indramayu Quadrangle; Geological Research and Development Centre: Bandung, Indonesia, 1992. [Google Scholar]
  29. Maria, R.; Rusydi, A.F.; Lestiana, H.; Wibawa, S. Hydrogeology and Groundwater Reserves in Indramayu. Ris. Geol. Pertamb. 2018, 28, 181–192. (In Indonesian) [Google Scholar]
  30. Rusydi, A.F.; Saito, M.; Ioka, S.; Maria, R.; Onodera, S.I. Estimation of ammonium sources in Indonesian coastal alluvial groundwater using Cl and GIS. Int. J. Geomate. 2019, 17, 53–58. [Google Scholar] [CrossRef]
  31. Koba, K.; Inagaki, K.; Sasaki, Y.; Takebayashi, Y.; Yoh, M. Nitrogen isotopic analysis of dissolved inorganic and organic nitrogen in soil extracts. Earth Life Isot. 2010, 17–36. [Google Scholar]
  32. Evans, R.D. Soil nitrogen isotope composition. In Stable Isotopes in Ecology and Environmental Science, 2nd ed.; Michener, R.H., Lajtha, K., Eds.; Blackwell Publishing: Oxford, UK, 2007; pp. 83–98. [Google Scholar] [CrossRef]
  33. Giblin, A.E.; Tobias, C.R.; Song, B.; Weston, N.; Banta, G.T.; Rivera-Monroy, V.H. The importance of dissimilatory nitrate reduction to ammonium (DNRA) in the nitrogen cycle of coastal ecosystems. Oceanography 2013, 26, 124–131. [Google Scholar] [CrossRef] [Green Version]
  34. Postawa, A.; Hayes, C.; Criscuoli, A.; Macedonio, F.; Angelakis, A.N.; Rose, J.B.; Maier, A.; McAvoy, D.C. Best Practice Guide on the Control of Iron and Manganese in Water Supply; IWA publishing: London, UK, 2013. [Google Scholar]
  35. Caschetto, M.; Robertson, W.; Petitta, M.; Aravena, R. Partial nitrification enhances natural attenuation of nitrogen in a septic system plume. Sci. Total Environ. 2018, 625, 801–808. [Google Scholar] [CrossRef]
  36. Kringel, R.; Rechenburg, A.; Kuitcha, D.; Fouépé, A.; Bellenberg, S.; Kengne, I.M.; Fomo, M.A. Mass balance of nitrogen and potassium in urban groundwater in Central Africa, Yaounde/Cameroon. Sci. Total Environ. 2016, 547, 382–395. [Google Scholar] [CrossRef] [Green Version]
  37. Appelo, C.A.J.; Postma, D. Geochemistry, Groundwater and Pollution, 2nd ed.; CRC Press: Boca Raton, FL, USA, 2005. [Google Scholar]
  38. Seitzinger, S.P.; Gardner, W.S.; Spratt, A.K. The effect of salinity on ammonium sorption in aquatic sediments: Implications for benthic nutrient recycling. Estuaries 1991, 14, 167–174. [Google Scholar] [CrossRef]
Figure 1. Land-use categories (a) and land-uses change from 2002 to 2019 (b) in Indramayu, Indonesia.
Figure 1. Land-use categories (a) and land-uses change from 2002 to 2019 (b) in Indramayu, Indonesia.
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Figure 2. Sampling points in the study site.
Figure 2. Sampling points in the study site.
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Figure 3. Geology (a) and vertical profile in the B–A cross section (b) of Indramayu, Indonesia (Completely redrawn and modified after Maria et al., 2018 [29]).
Figure 3. Geology (a) and vertical profile in the B–A cross section (b) of Indramayu, Indonesia (Completely redrawn and modified after Maria et al., 2018 [29]).
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Figure 4. Exchangeable NH4+ ratio (a,b), δ15N (c,d), %N (e,f), and cation exchange capacity (CEC) (g,h), in the sediments of the upper and lower coastal area.
Figure 4. Exchangeable NH4+ ratio (a,b), δ15N (c,d), %N (e,f), and cation exchange capacity (CEC) (g,h), in the sediments of the upper and lower coastal area.
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Figure 5. Concentrations of NO3–N and NH4+–N (mg/L) in the groundwater samples.
Figure 5. Concentrations of NO3–N and NH4+–N (mg/L) in the groundwater samples.
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Figure 6. Relationship of dissolved organic carbon (DOC) with NO3–N (a) and NH4+–N (b) in the groundwater samples.
Figure 6. Relationship of dissolved organic carbon (DOC) with NO3–N (a) and NH4+–N (b) in the groundwater samples.
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Figure 7. NH4+–N concentrations (mg/L) and δ15NNH4 values (‰) in the groundwater samples, and potential sources of NH4+–N based on δ15NNH4 values of several sources (ranges values of δ15NNH4 compositions for soil nitrogen, animal manure, and mineral fertilizer are adapted from Norrman et al., 2015 [6]; and for organic matter and household waste are adapted from Nikolenko et al., 2018 [19]).
Figure 7. NH4+–N concentrations (mg/L) and δ15NNH4 values (‰) in the groundwater samples, and potential sources of NH4+–N based on δ15NNH4 values of several sources (ranges values of δ15NNH4 compositions for soil nitrogen, animal manure, and mineral fertilizer are adapted from Norrman et al., 2015 [6]; and for organic matter and household waste are adapted from Nikolenko et al., 2018 [19]).
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Figure 8. Relationship of NH4+–N and Na+ (a), K+ (b), Mg2+ (c), Ca2+ (d) in groundwater samples.
Figure 8. Relationship of NH4+–N and Na+ (a), K+ (b), Mg2+ (c), Ca2+ (d) in groundwater samples.
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Figure 9. Average total major cations (a,b) (meq/L), NH4+ contents (meq/L) (c,d), and δ15NNH4 values (‰) (e,f) in three depths of groundwater in upper and lower coastal areas.
Figure 9. Average total major cations (a,b) (meq/L), NH4+ contents (meq/L) (c,d), and δ15NNH4 values (‰) (e,f) in three depths of groundwater in upper and lower coastal areas.
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Table 1. NH4+−N concentrations, δ15NNH4 values, and coliform bacteria.
Table 1. NH4+−N concentrations, δ15NNH4 values, and coliform bacteria.
SampleAquiferLocationNH4+−Nδ15NNH4Total ColiformE. coli
mmg/L(No./100 mL)
DH0125Upper coastal aquifer0.2UDNMNM
DH02163.159.21100150
DH0320.714.71100210
DH0732.4816.124002400
DH0841.873.72400210
DH0981.583.6210210
DH12120.32UDNMNM
DH13160.18UDNMNM
DH1452.339.5NMNM
DH1653.199.524001100
DH17100.07UDNMNM
DH1850.53UDNMNM
DH1960.427.524002400
DH23151.641.611000
DH2650.778.724003
DH27101.62−2.92400210
DH2950.973.524001100
DH3051.69524002400
Minimum0.42−2.9210 -
Maximum3.1916.12400 2400
Average1.646.11892866
DH0530Lower coastal aquifer12.972.924000
DH06202.354.0NMNM
DH102010.883.8NMNM
DH111004.211.8200
DH15802.791.970
DH22203.192.411000
DH24255.663.700
DH25208.262.324000
DH282011.812.2NMNM
DH3157.954.824000
Minimum2.35 1.8 00
Maximum14.60 4.8 24000
Average7.7 3.0 11900
NM = not measured; UD = under the detection limit.
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Rusydi, A.F.; Onodera, S.-I.; Saito, M.; Hyodo, F.; Maeda, M.; Sugianti, K.; Wibawa, S. Potential Sources of Ammonium-Nitrogen in the Coastal Groundwater Determined from a Combined Analysis of Nitrogen Isotope, Biological and Geological Parameters, and Land Use. Water 2021, 13, 25. https://doi.org/10.3390/w13010025

AMA Style

Rusydi AF, Onodera S-I, Saito M, Hyodo F, Maeda M, Sugianti K, Wibawa S. Potential Sources of Ammonium-Nitrogen in the Coastal Groundwater Determined from a Combined Analysis of Nitrogen Isotope, Biological and Geological Parameters, and Land Use. Water. 2021; 13(1):25. https://doi.org/10.3390/w13010025

Chicago/Turabian Style

Rusydi, Anna Fadliah, Shin-Ichi Onodera, Mitsuyo Saito, Fujio Hyodo, Morihiro Maeda, Khori Sugianti, and Sunarya Wibawa. 2021. "Potential Sources of Ammonium-Nitrogen in the Coastal Groundwater Determined from a Combined Analysis of Nitrogen Isotope, Biological and Geological Parameters, and Land Use" Water 13, no. 1: 25. https://doi.org/10.3390/w13010025

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