Coupled processes involving ammonium inputs, microbial nitrification, and calcite dissolution control riverine nitrate pollution in the piedmont zone (Qingshui River, China).

Rivers in agricultural countries widely suffer from diffuse nitrate (NO3-) pollution. Although pollution sources and fates of riverine NO3- have been reported worldwide, the driving mechanisms of riverine NO3- pollution associated with mineral dissolution in piedmont zones remain unclear. This study combined hydrogeochemical compositions, stable isotopes (δ18O-NO3-, δ15N-NO3-, δ18O-H2O, and δ2H-H2O), and molecular bioinformation to determine the pollution sources, biogeochemical evolution, and natural attenuation of riverine NO3- in a typical piedmont zone (Qingshui River). High NO3- concentration (37.5 ± 9.44 mg/L) was mainly observed in the agricultural reaches of the river, with ~15.38 % of the samples exceeding the acceptable limit for drinking purpose (44 mg/L as NO3-) set by the World Health Organization. Ammonium inputs, microbial nitrification, and HNO3-induced calcite dissolution were the dominant driving factors that control riverine NO3- contamination in the piedmont zone. Approximately 99.4 % of riverine NO3- contents were derived from NH4+-containing pollutants, consisted of manure & domestic sewage (74.0 % ± 13.0 %), NH4+-synthetic fertilizer (16.1 % ± 8.99 %), and soil organic nitrogen (9.35 % ± 4.49 %). These NH4+-containing pollutants were converted to HNO3 (37.2 ± 9.38 mg/L) by nitrifying bacteria, and then the produced HNO3 preferentially participated in the carbonate (mainly calcite) dissolution, which accounted for 40.0 % ± 12.1 % of the total riverine Ca2+ + Mg2+, also resulting in the rapid release of NO3- into the river water. Thus, microbial nitrification could be a new and non-negligible contributor of riverine NO3- pollution, whereas the involvement of HNO3 in calcite dissolution acted as an accelerator of riverine NO3- pollution. However, denitrification had lesser contribution to natural attenuation for high NO3- pollution. The obtained results indicated that the mitigation of riverine NO3- pollution should focus on the management of ammonium discharges, and the HNO3-induced carbonate dissolution needs to be considered in comprehensively understanding riverine NO3- pollution in piedmont zones.

Evaluating nitrate transport and accumulation in the deep vadose zone of the intensive agricultural region, North China Plain.

Evaluation of the nitrate transport process in the deep vadose zone (DVZ) is important for groundwater quality management, especially in intensive agricultural regions, such as the North China Plain (NCP). The NCP produces ~20% of the total food grain in China, owing to timely groundwater irrigation and excessive chemical N fertilizer applications, and faces severe groundwater environmental degradation. This study evaluated the potential impacts of intensive agriculture on groundwater quality by investigating nitrate accumulation and transport in the DVZ of wheat-maize double-cropping field based on sediment sampling (maximum depth of 45.2 m) over three sub-regions of the NCP. The results showed that legacy nitrate­nitrogen (NO3--N) accumulated in the DVZ ranged from 118.5 to 6302.8 kg N ha-1 across the NCP; it increased with depth at an average rate of ~157 kg ha-1 m-1. Nitrate transport and accumulation in the DVZ were spatially varied and mainly controlled by the DVZ sediment textures, in addition to water and nitrogen inputs from the ground surface. Coarse sediments retained lower soil water content, resulting in less nitrogen storage; however, they provided greater nitrate transport velocity. Higher transport velocities observed in the alluvial-proluvial fan allowed chemical N fertilizer to reach the water table. However, in other regions, nitrate transport velocities were lower than the water table decline rates, implying that groundwater quality may not have been impaired by chemical N fertilizer. Furthermore, a reductive environment was identified in some areas with fine sediments, indicating a favorable environment for denitrification in the DVZ. The findings of the current study could provide an important foundation for groundwater quality management in agricultural areas, such as the NCP and similar regions.

Quantifying impacts of climate dynamics and land-use changes on water yield service in the agro-pastoral ecotone of northern China.

Large-scale revegetation practices have lasted approximately two decades in the agro-pastoral ecotone of northern China (AENC), and their impacts on hydrological and ecological effects remain poorly understood. Previous studies largely focused on assessing water yield service (WYs) based on several fixed time points, whereas time series information-continuous WYs dynamics were more reliable and valuable in decision-making about water sustainability goals. This study analyzed the interannual WYs trend and relative roles of its drivers in the last 20 years based on a newly proposed approach, and revealed the past, present and future impacts of revegetation on WYs. The final results indicated that the annual WYs averaged approximately 97 mm and exhibited an increasing trend of 1.96 mm year-1 (p = 0.086) during 2000-2019, in which climate and land-use changes were responsible for 88% and 12% of WYs variations, respectively. From 2000 to 2019, WYs was pronouncedly 1.47 mm year-1 (p = 0.119) lower in the afforestation area than in the nonafforestation area, but the precipitation in the two regions had a statistically insignificant difference (p = 0.97). Future revegetation scenarios showed great potential for the shrinkage of WYs provision, even approaching a maximum of 50 mm at a local scale. Even so, the afforestation-induced reductions in blue water and benefits in green water both should receive equal attention. Specifically, any attempts to assess WYs or other climate-driven ecosystem services using discontinuous years as the study period must be taken with extreme caution.

[Hydrochemical Characteristics and Factors of Surface Water and Groundwater in the Upper Yongding River Basin].

The Yongding River basin is an important water conservation and ecological barrier area in the Northwest of Hebei Province. Reduced runoff and deterioration of the water environment in this area have become increasingly prominent under the effects of climate change and intensive human activities. Clarifying the chemical characteristics and factors of surface water and groundwater in the upper Yongding River basin can provide data and support for the sustainable use of water resources. Stable isotopes of hydrogen and oxygen (δ2H and δ18O) were used to study the sources of surface water and groundwater. Mathematical statistics and hydrogeochemical methods were then used to analyze the regional hydrogeochemical processes and factors of surface water and groundwater. The results showed that precipitation was the main source of surface water and groundwater. Under the effects of natural factors and human activities, the Yang River and Sanggan River basins exhibited significant differences in surface water chemistry. The sub-basins were ranked by ion concentration as follows: Sanggan River>Yang River. The main cation and anions of the Sanggan River basin were Na+, Cl-, and SO42-, while in the Yang River basin, Ca2+ and HCO3- were the most common. The water chemistry of the Sanggan River exhibited greater variation than that of the Yang River. Surface water chemistry were mainly controlled by mineral dissolution and evaporation, but human activities were reflected in different sub-basins. Surface water in the Sanggan River basin was affected by industrial wastewater discharge, while that of the Yang River basin was affected by agricultural production and cities. However, the continuous increase of Cl- and SO42- concentrations, caused by industrial wastewater discharge and acid rain, was the limiting factor for sustainable use of surface water resources. In future, surface water in Sanggan River basin should be used with consideration to the effects of both total salinity and chemical composition of the water, while in Yang River, a focus should be placed on total salinity. The use of surface water resources in accordance with local conditions is an effective measure for the sustainable use of water resources and the restoration of groundwater levels in this region.

Revegetation projects significantly improved ecosystem service values in the agro-pastoral ecotone of northern China in recent 20 years.

Revegetation is a conventional approach used for ecological protection and restoration projects, especially in the agro-pastoral ecotone of northern China (AENC). However, for this ecologically vulnerable area, the changes in land use and ecosystem service values (ESV) resulting from revegetation projects have received little attention and have not been fully elucidated. In this study, based on a rapid valuation tool-the benefit transfer method modified by the biomass factor (net primary productivity, NPP)-we assessed the ESV of the AENC at multiple-time scales by designing land scenarios related to local revegetation projects. The results showed that forestland expansion (+697 thousand ha) and grassland shrinkage (-650 thousand ha) dominated the land use change in the AENC in 2000-2018 and indirectly resulted in a net increase of US$8.18 billion in total ESV, in which revegetation projects generated nearly 1.5 million ha of new vegetated land and a corresponding US$6.86 billion in ESV (83.83% of the total increase). For future revegetation, the returning-farmland-to-forestland scenario exhibited a greater potential with increases of 5.66 million ha of forestland and US$65.20 billion in ESV to be provided. Overall, revegetation projects improved the ESV of the AENC in the last two decades because of the pronounced expansion in forestland of high ESV at the expense of the reductions in farmland and grassland, and this trend will be led continually by the Grain for Green Project in the future through the rapid assessment based on the modified benefit transfer method. Specifically, more investments and attention must be directed to the protection and restoration of grassland and wetland ecosystems.

Evaluation of the CropSyst Model during Wheat-Maize Rotations on the North China Plain for Identifying Soil Evaporation Losses.

The North China Plain (NCP) is a major grain production zone that plays a critical role in ensuring China's food supply. Irrigation is commonly used during grain production; however, the high annual water deficit [precipitation (P) minus evapotranspiration (ET)] in typical irrigated cropland does not support double cropping systems (such as maize and wheat) and this has resulted in the steep decline in the water table (~0.8 m year-1 at the Luancheng station) that has taken place since the 1970s. The current study aimed to adapt and check the ability of the CropSyst model (Suite-4) to simulate actual evapotranspiration (ETa), biomass, and grain yield, and to identify major evaporation (E) losses from winter wheat (WW) and summer maize (SM) rotations. Field experiments were conducted at the Luancheng Agro-ecosystem station, NCP, in 2010-2011 to 2012-2013. The CropSyst model was calibrated on wheat/maize (from weekly leaf area/biomass data available for 2012-2013) and validated onto measured ETa, biomass, and grain yield at the experimental station from 2010-2011 to 2011-2012, by using model calibration parameters. The revalidation was performed with the ETa, biomass, grain yield, and simulated ETa partition for 2008-2009 WW [ETa partition was measured by the Micro-lysimeter (MLM) and isotopes approach available for this year]. For the WW crop, E was 30% of total ETa; but from 2010-11 to 2013, the annual average E was ~40% of ETa for the WW and SM rotation. Furthermore, the WW and SM rotation from 2010-2011 to 2012-2013 was divided into three growth periods; (i) pre-sowing irrigation (PSI; sowing at field capacity) to emergence period (EP), (ii) EP to canopy cover period (CC) and (iii) CC to harvesting period (HP), and E from each growth period was ~10, 60, and 30%, respectively. In general, error statistics such as RMSE, Willmott's d, and NRMSE in the model evaluation for wheat ETa (maize ETa) were 38.3 mm, 0.81, and 9.24% (31.74 mm, 0.73, and 11.89%); for wheat biomass (maize biomass) they were 1.25 Mg ha-1, 0.83, and 9.64% (0.78 Mg ha-1, 0.96, and 7.96%); and for wheat grain yield (maize grain yield) they were 0.65 Mg ha-1, 0.82, and 9.87% (0.2 Mg ha-1, 0.99, and 3.79%). The results showed that CropSyst is a valid model that can be use with a reliable degree of accuracy for optimizing WW and SM grain yield production and water requirement on the NCP.

[Nitrogen and water cycling of typical cropland in the North China Plain].

Intensive fertilization and irrigation associated increasing grain production has led to serious groundwater depletion and soil/water pollution in the North China Plain (NCP). Intensive agriculture changes the initial mass and energy balance, and also results in huge risks to the water/soil resources and food security regionally. Based on the research reports on the nitrogen cycle and water cycle in typical cropland (winter wheat and summer corn) in the NCP during the past 20 years, and the meteorological data, field experiments and surveys, we calculated the nitrogen cycle and water-cycle for this typical cropland. Annual total nitrogen input were 632 kg N . hm-2, including 523 kg N . hm-2 from commercial fertilizer, 74 kg N . hm-2 from manure, 23 kg N . hm-2 from atmosphere, and 12 kg N . hm-2 from irrigation. All of annual outputs summed to 532 kg N . hm-2 including 289 kg N . hm-2 for crop, 77 kg N . hm-2 staying in soil profile, leaching 104 kg N . hm-2, 52 kg N . hm-2 for ammonia volatilization, 10 kg N . hm-2 loss in nitrification and denitrification. Uncertainties of the individual cases and the summary process lead to the unbalance of nitrogen. For the dominant parts of the field water cycle, annual precipitation was 557 mm, irrigation was 340 mm, while 762 mm was for evapotranspiration and 135 mm was for deep percolation. Considering uncertainties in the nitrogen and water cycles, coupled experiments based on multi-disciplines would be useful for understanding mechanisms for nitrogen and water transfer processes in the soil-plant-atmosphere-continuum (SPAC) , and the interaction between nitrogen and water, as well as determining the critical threshold values for sustainability of soil and water resources in the NCP.