Revealing the drivers and genesis of NO3-N pollution classification in shallow groundwater of the Shaying River Basin by explainable machine learning and pathway analysis method.

Nitrate (NO3-N), as one of the ubiquitous contaminants in groundwater worldwide, has posed a serious threat to public health and the ecological environment. Despite extensive research on its genesis, little is known about the differences in the genesis of NO3-N pollution across different concentrations. Herein, a study of NO3-N pollution concentration classification was conducted using the Shaying River Basin as a typical area, followed by examining the genesis differences across different pollution classifications. Results demonstrated that three classifications (0-9.98 mg/L, 10.14-27.44 mg/L, and 28.34-136.30 mg/L) were effectively identified for NO3-N pollution using Jenks natural breaks method. Random forest exhibited superior performance in describing NO3-N pollution and was thereby affirmed as the optimal explanatory method. With this method coupling SEMs, the genesis of different NO3-N pollution classifications was proven to be significantly different. Specifically, strongly reducing conditions represented by Mn2+, Eh, and NO2-N played a dominant role in causing residual NO3-N at low levels. Manure and sewage (represented by Cl-) leaching into groundwater through precipitation is mainly responsible for NO3-N in the 10-30 mg/L classification, with a cumulative contribution rate exceeding 80 %. NO3-N concentrations >30 mg/L are primarily caused by the anthropogenic loads stemming from manure, sewage, and agricultural fertilization (represented by Cl- and K+) infiltrating under precipitation in vulnerable hydrogeological conditions. Pathway analysis based on standardized effect and significance further confirmed the rationality and reliability of the above results. The findings will provide more accurate information for policymakers in groundwater resource management to implement effective strategies to mitigate NO3-N pollution.

Effect and genesis of soil nitrogen loading and hydrogeological conditions on the distribution of shallow groundwater nitrogen pollution in the North China Plain.

The North China Plain (NCP) has experienced increasingly severe groundwater nitrogen (TN) pollution. However, the factors influencing TN distribution are still poorly understood. Previous studies have identified surface soil nitrogen (TSN) loading and intrinsic groundwater vulnerability (Inv) as the main factors controlling groundwater TN pollution. However, in this study, based on 3245 shallow groundwater samples in the NCP, the multiple regression analysis results(R2=0.105, p<0.001) revealed that the TN was not mainly controlled by TSN and Inv. The lower prediction accuracy indicated the large data dispersion of TN, which might be affected by nitrogen attenuation or accumulation. Thus, the NCP was divided into balance, attenuation, and accumulation zones according to the regression equation. The attenuation zone was mainly distributed in the inter-fan and fan edge parts of the pre-mountain alluvial floodplain, as well as the west and south of the runoff area, while the accumulation zone was mainly distributed in the top part of the pre-mountain alluvial floodplain and the east of discharge area. Multi-indicators comparative analysis showed that compared to the balance (Eh= 76.2 mV) and accumulation (Eh=126.7 mV) zones, the attenuation zone has a stronger reducing environment (Eh=30.8 mV) favorable to denitrification, which can reduce the TN pollution (0.49 mg/L) caused by surface nitrogen input and consume more electron donors. Conversely, the stronger oxidizing environment in the accumulation zone limited denitrification, resulting in higher TN concentrations (19.14 mg/L) in the aquifers under the same TSN and Inv conditions as the other two zones. The standardized effects and significance on each path of the structural equation model (SEMs) fully confirmed the reliability of the above zonal analysis. Importantly, the feature importance (23.6%) of random forest and standardized effects (0.455, p<0.001) of SEMs showed that the Eh had the strongest influence on TN. Thus, the redox conditions of the aquifer, in addition to TSN and Inv, played a crucial role in controlling the TN pollution in the groundwater of a large region. The zoning work and the analysis of influencing factors are important to guide scientific prevention and control of groundwater nitrogen pollution.

Water with low ionic strength recovers the passivated birnessite-coated sand reactivity towards lincomycin removal.

The ionic strength of infiltration water changes with the seasonal alternation of irrigation sources. In this study, reactivity changes of birnessite-coated sand with the fluctuations of ionic strength of infiltration water (i.e. from groundwater to rainwater) and the involved mechanism were investigated through column experiments. Birnessite-coated sand was less reactive in groundwater than in rainwater because of the higher cation content and higher pH of groundwater. The cations in the groundwater were adsorbed on birnessite-coated sand and then desorbed in presence of a dilute aqueous solution represented by rainwater. The reactivity of the passivated birnessite-coated sand was recovered instantaneously, and approximately one-third of the pristine reactivity was restored. During recovery, Na+ desorption and lincomycin (LIN) removal both exhibited a two-stage reaction pattern. The LIN removal correlated with Na+ desorption (r = 0.99) so that the reactive sites that were binding 5.602 µmol of Na+ became available for 1 µmol of LIN removal. These results suggest that the reactivity of manganese oxides toward organic contaminant is associated with the ionic strength of infiltration water and indicate that the partial reactivity can be naturally restored.

Arsenic mobilization in aquifers of the southwest Songnen basin, P.R. China: evidences from chemical and isotopic characteristics.

High As groundwater has widely been found in the inland basins of China. Little is known about distribution and mobilization mechanisms of high As groundwater in the Songnen basin, where groundwater is the major source for drinking and irrigation. Eighty-seven groundwater samples, three surface water samples and sixty-three sediment samples were taken from the southwest of the Songnen basin, in order to investigate spatial distribution and constrains of groundwater As. Results showed that high As groundwater was generally of Na-Mg/Ca-HCO3 type, which had relatively low Eh values and neutral-weakly alkaline pH. High As groundwater was characterized by low concentrations of NO3(-) and SO4(2-), and high concentrations of Fe, Mn, and H2S. Around 65.5% of sampled shallow groundwater and 96% of sampled deep groundwater had As concentrations greater than 10 µg/L. Sediments had higher total As contents and higher Fe/Mn oxide-bound As contents in high As groundwater area than in the low As groundwater area. Distribution of groundwater As was dependent upon hydrogeologic settings, redox potential, microbial degradation of organic carbon, and precipitation of pyrite, siderite, and calcite. Along the groundwater flow path, As concentration showed an increasing trend. High As groundwater was mainly distributed in the low-lying areas. Reducing conditions were the major causes for As mobilization in the aquifers, which led to more As released from the sediments with higher contents of Fe/Mn oxide-bound As in higher As groundwater area. Results of (13)CDOC and (13)CDIC showed that dissimilatory Fe(III) reduction coupled with microbial degradation of dissolved organic carbon would be related to As mobilization in the aquifers. Although both Fe and As were released during these redox processes, pyrite, siderite and calcite precipitation would be the sink of dissolved As, which resulted in weak correlation between dissolved Fe and As.

Abnormally high ammonium of natural origin in a coastal aquifer-aquitard system in the Pearl River Delta, China.

High-nitrogen loadings of rivers and aquifers systems are a major concern because of potential effects on human health and water quality impacts such as eutrophication of lakes and coastal zones. This nitrogen enrichment is commonly attributed to anthropogenic sources such as sewage and agricultural and industrial wastes. The aims of this study were to delineate spatial distribution of groundwater ammonium in the coastal aquifer system in Pearl River Delta (PRD), China and to identify the origin of the abnormally high ammonium. A total of 40 boreholes were drilled to collect core samples of the aquitard and groundwater samples in the basal aquifer. The core samples were used for extraction of pore water for centrifugation and bulk chemical analyses in laboratory. Unlike previous studies which focused mainly on the aquifer, this study treated the aquifer-aquitard system as a hydrogeochemical continuum. The results show that the aquifer-aquitard system contains an exceptionally large total ammonium mass. Ammonium occurred at concentrations up to 390 mg/L in the basal sand Pleistocene aquifer 20-50 m deep, the largest concentration reported for groundwater globally. This ammonium was natural, areally extensive (1600 km(2)) and originated in the overlying Holocene-Pleistocene aquitard and entered the aquifer by groundwater transport and diffusion. Total ammonium in the aquifer (190 × 10(6) kg) was exceeded by total ammonium in the aquitard (8600 × 10(6) kg) by a factor of 45. Much organic nitrogen remained in the aquitard available for conversion to ammonium. This natural ammonium in the aquifer was slowly transported into the PRD river channels and the estuary of the South China Sea. The rate of this contribution will likely be greatly increased by sand dredging in the river channels and estuary. Although the ammonium in PRD groundwater occurred in the largest concentrations and mass reported globally, the literature shows no reports of other delta aquitards having been examined for ammonium occurrence and therefore abundant ammonium formed in aquitards rich in organic matter may not be uncommon and this "geologic" source of ammonium may present a large and hitherto unappreciated source of nitrogen discharging to surface waters.