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In this study, the sources causing high concentrations of NO3- and NH4+ in

groundwater, the transformation within N-budget system of the sources, the contribution

of nitrogen compounds to the release of As into groundwater, and the simulations of N

transformation and transport in As-rich groundwater of Choushui river alluvial fan have

been identified.

First, the results obtained for δ15NNO3 and δ18ONO3 suggest that NO3 denitrification

by microorganisms may occur from the upstream region to the downstream region of the

Choushui River. The NO3 concentrations decrease in the downstream direction.

The sources of NO3 in the proximal fan of the Choushui River alluvial fan may be

ammonium fertilizers, soil ammonium, and manure and septic waste. Because the

groundwater tends to be oxidative, NH4+ is converted to NO3 (nitrification) once the

NH4+ sources infiltrate the groundwater, resulting in the enrichment of NO3. However,

there is no clear evidence for NO3 assimilation by living organisms or NO3

denitrification by microorganisms in the proximal fan.

The physicochemical characteristics and the relatively low value of δ18ONO3 in the

proximal fan of the Choushui River alluvial fan indicates the possibility of oxygen from

sources other than NO3

entering the groundwater. Atmospheric oxygen serves as an

alternative to the oxygen in NO3 for microbial activities. The entry of atmospheric

oxygen results from unconfined granular nature and overpumping of groundwater for

agricultural activities.

The lnNO3 versus δ15NNO3 plot for the mid-fan of the Choushui River alluvial fan

suggests that NO3 assimilation and denitrification may occur in the groundwater.

However, the ratio δ15N/δ18O shows only mild denitrification, suggesting that NO3

assimilation by living organisms, rather than denitrification, is dominant and responsible

for the depletion of NO3

. The environment of high concentrations of As, NH4+ and Fe,

and the depletion of δ15NNO3 suggest the occurrence of feammox process in the mid-fan,

causing As to desorb from Fe oxyhydroxides and release to groundwater.

The NO3 sources in the mid-fan and the distal fan of the Choushui River alluvial fan

appear to be nitrate fertilizers and marine nitrate. NO3 is assimilated and mineralized to

NH4+ by heterorganic microbes or through DNRA in the reductive groundwater, leading

to the enrichment of NH4+ in the groundwater. The lnNO3 versus δ15NNO3 plot shows the

possibility of NO3 assimilation and denitrification in the groundwater. The ratio

δ15N/δ18O in the distal fan indicates that NO3 denitrification is significant, and the

enrichment of both 15NNO3 and 18ONO3 support this indication. In other words, assimilation,

mineralization, DNRA, and denitrification should occur simultaneously in the distal fan

of the Choushui River alluvial fan, resulting in the depletion of NO3 and enrichment of

NH4+ in the groundwater.

High NO3 concentrations in the groundwater of the proximal fan result in an

oxidative environment, which is not favorable for the reductive dissolution of

As-containing Fe oxyhydroxides. By contrast, feammox in the mid-fan and denitrification in

the distal fan may lead to the reductive dissolution of As-containing Fe oxyhydroxides,

resulting in the release of As into the groundwater; because of the reductive environment,

NH4+ and As are present in considerable amounts.

Furthermore, the PHREEQC simulation suggested that 92.31% of NH4+ in the

proximal fan, 69.70% of NH4+ in the mid-fan, and 21.17% of NH4+ in the distal fan

simulatively oxidized to NO3 through nitrification and/or feammox. These data clearly

show that the nitrification and/or Feammox mostly occur in the proximal fan and

mid-fan, whereas they slightly occur in the distal fan. The reaction of nitrification leads to the

consequence of groundwater being abundant in NO3 and being depleted in NH4+. The

mean concentrations of NO3 and NH4+ in the proximal fan are 23.62 mg/L and 0.17 mg/L,

respectively, evidently supporting the occurrence of NH4+ nitrification. Also, the

proximal fan was assessed on the basis of local DO and ORP values to be in an oxidative

state, initiatively urging the occurrence of nitrification.

32.93% of NO3

in the mid-fan and 61.13% of NO3

in the distal fan simulatively

reduced to N2 or NH4+ through denitrification and/or DNRA. The spatial concentration

distribution of NO3 from the proximal fan to the distal fan indicates the gradual

occurrence of NO3 denitrification and/or DNRA from upstream to downstream of the

Choushui River alluvial fan. Also, the mid-fan and the distal fan were assessed on the

basis of the local DO and ORP values to be in relatively more reductive conditions,

driving the occurrence of denitrification and/or DNRA. Moreover, the concentration of

NH4+ in the distal fan indicates that in addition to denitrification, DNRA might be the

dominant process of N cycling in the distal fan.

In the proximal fan, As3+ decreased by 1.32E−4 mg/L, and this valence

transformation of As species and As concentration difference seem comprehensible. In

the mid-fan and the distal fan, the reductive state was observed base on the DO and ORP

data of the groundwater, and the circumstance of reduction from As5+ to As3+ was

obvious, reaching 6.62E−3 mg/L and 6.40E−3 mg/L, respectively.

The discrepancy of δ15N in NO3

in groundwater was simulated on the basis of the

influence of the reaction of NO3 denitrification. The values of δ15NNO3 in the

groundwater of the mid-fan and the distal fan increased by +2.11% and +5.79%,

respectively. The δ15N value of the residual NO3

increases with a decrease in the NO3

concentration during denitrification. Further, the reductive environment further enhances

the reductive dissolution of As-bearing Fe oxyhydroxides and the desorption of adsorbed

As, resulting in the release of As into groundwater.

The 1-D transport simulation result suggested that NO3 assimilation occur from the

mid-fan of the Choushui River Alluvial Fan to the distal fan, whereas NH4+ nitrification

is observed at the beginning of the proximal fan. The initial and twenty-five years of NO3

and NH4+ transport have little shift backward but are insignificant.

The total amount of As increased along the upstream to the downstream of the

Choushui River. The concentration of As5+increased at the beginning of the mid-fan,

which may be caused by the reductive dissolution of As-bearing Fe oxyhydroxides and

the desorption of adsorbed As. The concentration of As3+ increased obviously at the

beginning of the distal fan, which may be related to the transformation of As5+to As3+ in

the reductive environment, and the continuous desorption of As from Fe oxyhydroxides

simultaneously.

Both the concentrations of Fe3+ and Fe2+ increased at the end of proximal, causing

by the reductive dissolution of Fe oxyhydroxides. The transformation of Fe3+ to Fe2+

occurred soon when the groundwater reached the mid-fan, resulting in depletion of Fe3+

and increase in Fe2+ in groundwater. The increase in Fe2+ is not only related to the

reductive environment, but also attributed to the reaction of feammox, which Fe

oxyhydroxides react with NH4+ and produce Fe2+ in the groundwater.

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