Influences of Nitrogen Cycle on Arsenic Enrichment in Shallow Groundwater from the Yellow River Alluvial Fan Plain
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摘要:
黄河冲积扇平原浅层地下水砷含量超标情况严重，豫北平原的主体是黄河冲洪积扇平原。全面了解豫北平原浅层地下水氮循环驱动下砷的富集模式，对地下水资源的可持续利用和居民健康至关重要。本文采集豫北平原513组浅层地下水样品，采用原子荧光光谱法测定砷含量，原子吸收光谱和离子色谱等方法进行全分析及微量元素分析，对该地区高砷地下水的水化学成分以及地下水中硝酸盐、氨氮与砷之间的相关关系进行探究，并研究了氮循环对地下水中砷迁移富集的影响。结果表明：研究区浅层地下水中砷浓度超标率为17.3%。不同沉积环境条件下氮的赋存形态和转化方式是砷富集的重要驱动因素。山前冲洪积扇裙带中经硝化作用产生大量NO3-，浓度平均值为9.3mg/L，为各区最高，同时砷浓度为各区最低，平均值为1.3μg/L，NO3-与砷浓度之间良好的负相关性表明硝化作用产生大量NO3-，不利于含砷氧化铁的溶解；NH4+含量较高的冲洪积扇前洼地及黄河决口扇地区，为高砷地下水的聚集地，两地地下水砷浓度平均值分别为49.7μg/L和18.9μg/L，超标率达到87.5%和71.4%。地下水中砷含量与NH4+之间良好的正相关关系表明，反硝化和硝酸异化还原成铵（DNRA）过程消耗了地下水中的NO3-，生成大量NH4+，促进吸附了砷的铁氧化物的还原溶解而导致砷释放到地下水中，形成了富集砷的环境。
Abstract:BACKGROUND Arsenic content in shallow groundwater of the Yellow River alluvial fan plain exceeds the standard. A comprehensive understanding of the arsenic enrichment mode driven by the nitrogen cycle of shallow groundwater in the northern Henan Plain is essential for the sustainable use of groundwater resources and the health of residents. The main area of the North Henan plain is the Yellow River alluvial fan plain. The sedimentary environment in the northern Henan plain is complex, and is influenced by the Yellow River breach, diversion and oscillation, as well as alluvial diluvial in the mountainous area around the basin. The distribution, migration and release mechanism of As, NH4+ and NO3- are quite different under different sedimentary environment conditions. The joint enrichment mechanism of the three is still unclear, which is worth further study.
OBJECTIVES To investigate the effect of nitrogen cycling on arsenic migration and enrichment in groundwater in the Northern Henan Plain.
METHODS 513 shallow groundwater samples were collected from the northern Henan Plain. Atomic fluorescence spectroscopy was used to determine the arsenic content, atomic absorption spectroscopy and ion chromatography, and other methods for major and trace element analysis. The correlation between nitrate, ammonia nitrogen and arsenic was investigated, and the influence of nitrogen cycle on the migration and enrichment of arsenic in groundwater was studied.
RESULTS The over-standard rate of arsenic concentration in shallow groundwater in the study area was 17.3%. The occurrence and transformation modes of nitrogen under different depositional environmental conditions were important driving factors for arsenic enrichment. A large amount of NO3- was produced by nitrification in the groundwater of the alluvial fan in the piedmont alluvial fan, which had the average concentration of 9.3mg/L and was the highest in the district. At the same time, the concentration of arsenic was the lowest in the district, with the average of 1.3μg/L. The good negative correlation between NO3- and As concentration indicated that nitrification produced a large amount of NO3-, which was not conducive to the dissolution of arsenic-containing iron oxide. The depressions in front of the alluvial fan and the Yellow River crater fan with higher NH4+ content were the gathering places of high-arsenic groundwater. The average concentration of arsenic in groundwater from these two areas was 49.7μg/L and 18.9μg/L, respectively, and the exceeding rate reached 87.5% and 71.4%. The good positive correlation between arsenic content and NH4+ in groundwater indicated that the process of denitrification and dissimilative reduction of nitric acid to ammonium (DNRA) consumed NO3- in groundwater and generated a large amount of NH4+, which promoted the reduction and dissolution of iron oxides that adsorbed arsenic, forming an environment rich in arsenic.
CONCLUSIONS The nitrogen cycle plays an important role in the migration and enrichment of arsenic. The migration and enrichment mode of arsenic driven by the nitrogen cycle provides a scientific basis for the treatment and supervision of groundwater with high arsenic content.
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表 1 地下水主要化学组分统计特征
Table 1. Statistical characteristics of major chemical composition of groundwater
研究区(n=513) pH TDS (mg/L) Eh (mg/L) NO3- (mg/L) NH4+ (mg/L) Fe2+ (mg/L) As (μg/L) 最小值 6.1 271.3 -281.0 ＜0.01 ＜0.016 ＜0.04 ＜0.1 最大值 8.4 7825.0 337.0 239.4 2.82 14.8 190.0 平均值 7.4 1012.2 -9.0 3.8 0.18 1.4 7.4 中值 7.4 797.0 -23.0 0.1 0.03 0.7 2.2 SD 0.3 782.0 122.9 13.4 0.69 1.8 17.5 CV 0.04 0.8 -13.7 3.6 3.8 1.3 2.4 A区(n=164) pH TDS (mg/L) Eh (mg/L) NO3- (mg/L) NH4+ (mg/L) Fe2+ (mg/L) As (μg/L) 最小值 6.9 271.3 -245.0 ＜0.01 ＜0.016 ＜0.04 ＜0.1 最大值 8.3 5561.0 337.0 68.2 1.2 4.2 16.0 平均值 7.4 1006.0 83.4 9.3 0.04 0.4 1.3 中值 7.4 800.5 96.0 5.2 0.02 0.1 0.5 SD 0.3 699.2 101.9 12.9 0.12 0.7 2.1 CV 0.04 0.7 1.2 1.4 2.6 1.7 1.7 B区(n=262) pH TDS (mg/L) Eh (mg/L) NO3- (mg/L) NH4+ (mg/L) Fe2+ (mg/L) As (μg/L) 最小值 6.1 326.0 -281.0 ＜0.01 ＜0.016 ＜0.04 ＜0.1 最大值 8.4 7825.0 308.0 239.4 2.3 14.8 91.0 平均值 7.4 1100.4 -44.5 1.4 0.13 1.6 4.6 中值 7.4 844.5 -53.5 0.1 0.05 0.9 2.6 SD 0.3 918.2 113.6 14.8 0.26 2.0 7.6 CV 0.05 0.8 -2.6 10.3 2.1 1.2 1.7 C区(n=24) pH TDS (mg/L) Eh (mg/L) NO3- (mg/L) NH4+ (mg/L) Fe2+ (mg/L) As (μg/L) 最小值 7.0 431.0 -229.0 0.03 ＜0.016 ＜0.04 ＜0.1 最大值 8.0 1151.5 127.0 4.7 2.82 9.3 190.0 平均值 7.5 752.9 -105.7 0.6 1.27 3.6 49.7 中值 7.4 738.0 -124.0 0.3 0.50 2.8 21.0 SD 0.2 221.8 78.9 1.0 2.81 2.7 55.2 CV 0.03 0.3 -0.7 1.6 2.2 0.7 1.1 D区(n=63) pH TDS (mg/L) Eh (mg/L) NO3- (mg/L) NH4+ (mg/L) Fe2+ (mg/L) As (μg/L) 最小值 6.9 361.0 -261.0 0.05 ＜0.016 ＜0.04 ＜0.1 最大值 7.9 1990.4 121.0 17.6 2.7 4.8 64.0 平均值 7.5 760.1 -64.9 0.4 0.34 1.9 18.9 中值 7.6 690.8 -85.0 0.04 0.22 2.0 16.0 SD 0.2 271.7 78.2 2.2 0.40 1.0 13.6 CV 0.03 0.4 -1.2 5.5 1.2 0.6 0.7 注：SD为标准差; CV为变异系数; CV=SD/平均值。 
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