Evaluation of Phosphorus Enrichment in Groundwater by Legacy Phosphorus in Orchard Soils with High Phosphorus Adsorption Capacity Using Phosphate Oxygen Isotope Analysis.

Long-term phosphorus (P) fertilization results in P accumulation in agricultural soil and increases the risk of P leaching into water bodies. However, evaluating P leaching into groundwater is challenging, especially in clay soil with a high P sorption capacity. This study examined whether the combination of PO4 oxygen isotope (δ18OPO4) analysis and the P saturation ratio (PSR) was useful to identify P enrichment mechanisms in groundwater. We investigated the groundwater and possible P sources in Kubi, western Japan, with intensive citrus cultivation. Shallow groundwater had oxic conditions with high PO4 concentrations, and orchard soil P accumulation was high compared with forest soil. Although the soil had a high P sorption capacity, the PSR was above the threshold, indicating a high risk of P leaching from the surface orchard soil. The shallow groundwater δ18OPO4 values were higher than the expected isotopic equilibrium with pyrophosphatase. The high PSR and δ18OPO4 orchard soil values indicated that P leaching from orchard soil was the major P enrichment mechanism. The Bayesian mixing model estimated that 76.6% of the P supplied from the orchard soil was recycled by microorganisms. This demonstrates the utility of δ18OPO4 and the PSR to evaluate the P source and biological recycling in groundwater.

Assessment of nitrogen budget in detailed spatial pattern using high precision modeling approach with constructed accurate agricultural behavior.

Changes in the nitrogen cycle due to fertilizer use can cause severe environmental pollution, particularly groundwater pollution, and threaten biosphere integrity. There are many difficulties and limitations in assessing groundwater pollution and a detailed nitrogen budget in an agricultural catchment. Previous methodologies have failed in an accurate assessment of the nitrogen budget in detailed spatial patterns. Herein, we designed a new modeling approach to assess the nitrogen budget using detailed spatial patterns in an agricultural catchment in the Nara Basin. We revised the Soil and Water Assessment Tool file output format, added the results for river nutrient concentrations and ammonia volatilization to the original output file. In this study, we calibrated and validated crop harvests, paddy evapotranspiration, streamflow, and river water concentrations of nitrate-nitrogen and total nitrogen to improve model accuracy as much as possible. Among them, data for evapotranspiration was obtained from a newly released Landsat dataset. The results showed that the amount of nitrogen leaching in rice paddies was 42 kg/ha, accounting for 65 % of total leaching in the study catchment. Cambisols and Fluvic Gleysols were prone to denitrification, and nitrogen leaching or denitrification occurred relatively more readily in low-slope areas. Furthermore, a detailed analysis of nitrogen cycle processes with high spatial precision indicates that areas with severe surface water pollution may also exhibit significant groundwater pollution. Our findings provide new solutions for assessing the nitrogen budget and groundwater pollution in catchments.

Spatial and temporal dynamics and fluxes estimation of manganese fractions in sediments from the Pearl River Estuary, southern China.

Sequential extraction was used to study the historical dynamics and fluxes of the chemical fractions of manganese (Mn) in sediments collected from the Pearl River Estuary (PRE), southern China. Results revealed that the proportion of Mn associated with different fractions decreased in the order of acid-soluble fraction (F1) > reducible fraction (F2) > residual fraction (F4) > oxidizable fraction (F3). F1 (47%) was the dominant Mn fraction, indicating the strong bioavailability of Mn to aquatic organisms in the PRE. In addition, the Mn fraction F2 was present at an average rate of 27.93 % in surface sediments, indicating that it could be mobilized when environmental conditions become increasingly reducing or oxidizing. The decline in Mn fraction fluxes after 2006 indicated that the region has partially decreased due to the removal of heavily polluting industries and effective control of sewage discharge.

Spatial and Temporal Variations and Risk Assessment of Heavy Metal Fractions in Sediments of the Pearl River Estuary, Southern China.

Sequential extraction was used to study the mobility and ecological risk of chemical fractions of six heavy metals in sediments collected from the Pearl River Delta (PRE) in China. Results revealed that residual fractions (F4) were the dominant forms for Cr and Ni in surface sediments, indicating that they were primarily stable in nature and had low bioavailability and ecotoxicity. Cd had a high environmental risk owing to its higher availability in acid-soluble fraction (F1), whereas Pb occurred predominantly in the reducible fraction (F2) in surface sediments. The profile variations of bioavailable fractions were generally consistent with socioeconomic development in the Pearl River Delta (PRD). A decreasing trend after 2006 suggested a reduction in heavy metal bioavailable fractions owing to the removal of heavy polluting industries and the effective control of sewage discharge. The risk assessment code suggested that the high mobility of Cd posed an extremely high risk and a threat to the aquatic environment.

A new sampling method with zirconium-loaded resin for phosphate oxygen isotope analysis in oligotrophic freshwater systems.

RATIONALE: The phosphate oxygen isotope ratio ( δ 18 O PO 4 ) is a useful technique to trace the sources and biogeochemical cycles of phosphorus (P) in aquatic ecosystems. However, δ 18 O PO 4 has not been widely used in oligotrophic freshwater systems due to technical and methodological difficulties in collecting sufficient phosphate (PO4 ) for the δ 18 O PO 4 analysis, which sometimes requires hundreds of liters of the water sample. In this study, a new approach (PaS-Zir) was developed for the δ 18 O PO 4 analysis in oligotrophic freshwater systems using zirconium (Zr)-loaded (ZrIRC) resin, which has a high affinity for PO4 . METHODS: ZrClO2 was added to Amberlite IRC748 to obtain the ZrIRC resin. The adsorption/desorption experiment using KH2 PO4 with a known value of δ 18 O PO 4 was conducted to determine the adsorption/desorption properties of the resin and the likelihood of isotopic fractionation. By installing mesh bags filled with the resin, the PaS-Zir approach was used in two rivers with low PO4 concentrations (0.2 and 5.3 µmol/L). A conventional sampling method was also performed in the study river with a higher PO4 concentration to validate the efficacy of the PaS-Zir method. RESULTS: The adsorption/desorption experiment demonstrated that the ZrIRC resin possessed a sufficient adsorption capacity (153 µmol/resin-mL) and exhibited little isotopic fractionation during the adsorption/desorption processes. Using the PaS-Zir method, we were able to collect sufficient PO4 samples for the δ 18 O PO 4 analysis from the rivers within at least 4 days of mesh bag installation. The δ 18 O PO 4 values (14.2‰ ± 0.2‰) obtained using the PaS-Zir method were comparable to those obtained using the conventional method (14.0‰ ± 0.03‰). CONCLUSION: We proved that the PaS-Zir method is applicable to oligotrophic freshwater systems and is generally more efficient than the conventional method. In addition, our method is useful for improving the understanding of the P dynamics of oligotrophic ecosystems because of the extremely low concentration of PO4 commonly found in them, which are often prone to P pollution.

A new method for phosphate purification for oxygen isotope ratio analysis in freshwater and soil extracts using solid-phase extraction with zirconium-loaded resin.

RATIONALE: Phosphate (PO4 ) oxygen isotope (δ18 OPO4 ) analysis is increasingly applied to elucidate phosphorus cycling. Due to its usefulness, analytical methods continue to be developed and improved to increase processing efficiency and applicability to various sample types. A new pretreatment procedure to obtain clean Ag3 PO4 using solid-phase extraction (SPE) with zirconium-loaded resin (ZrME), which can selectively adsorb PO4 , is presented and evaluated here. METHODS: Our method comprises (1) PO4 concentration, (2) PO4 separation by SPE, (3) cation removal, (4) Cl- removal, and (5) formation of Ag3 PO4 . The method was tested by comparing the resulting δ18 OPO4 of KH2 PO4 reagent, soil extracts (NaHCO3 , NaOH, and HCl), freshwater, and seawater with data obtained using a conventional pretreatment method. RESULTS: PO4 recovery of our method ranged from 79.2% to 97.8% for KH2 PO4 , soil extracts, and freshwater. Although the recovery rate indicated incomplete desorption of PO4 from the ZrME columns, our method produced high-purity Ag3 PO4 and accurate δ18 OPO4 values (i.e., consistent with those obtained using conventional pretreatment methods). However, for seawater, the PO4 recovery was low (1.1%), probably due to the high concentrations of F- and SO4 2- which interfere with PO4 adsorption on the columns. Experiments indicate that the ZrME columns could be regenerated and used repeatedly at least three times. CONCLUSIONS: We demonstrated the utility of ZrME for purification of PO4 from freshwater and soil extracts for δ18 OPO4 analysis. Multiple samples could be processed in three days using this method, increasing sample throughput and potentially facilitating more widespread use of δ18 OPO4 analysis to deepen our understanding of phosphorus cycling in natural environments.

Assessment of long-term phosphorus budget changes influenced by anthropogenic factors in a coastal catchment of Osaka Bay.

Phosphorus usage is irreplaceable in agriculture; however, its excessive use leads to wastage of invaluable resources and significant soil surplus. Agronomic soil phosphorus surplus in Asian regions has a much higher level than the global average. And with rapid urbanization and population growth in the recent decades, Asian countries have seen a rise in environmental pollution levels also. This study assessed the detailed phosphorus budget in the Yamato River catchment, an urbanized coastal catchment in Asia, from 1940s to 2010s using Soil and Water Assessment Tool, comprehensively analyzed the effect of anthropogenic factors on long-term phosphorus loading and agronomic soil phosphorus balance. The results showed the peak period of total phosphorus loading and agronomic soil phosphorus surplus occurred in 1970s, at 895 tons/year and 36.6 kg/ha, respectively. The major reasons for increased phosphorus loading and soil surplus during 1940-1970 were rapid population growth and increased fertilizer usage, respectively. Since the 1980s, the construction of wastewater treatment system and reduction in agricultural land contributed to environmental improvement. These anthropogenic factors had a much stronger impact on phosphorus budget than climate change in the study catchment. Soil phosphorus balance is affected by a combination of factors, such as soil properties, fertilizer usage and applied schedule, precipitation event, and crop types. And soil phosphorus surplus may be severely overestimated if the non-point source loss due to precipitation factor is not fully considered.

Effects of forest growth in different vegetation communities on forest catchment water balance.

Forest ecosystems are critical for adjusting the dynamic balance of the hydrological cycle. This balance is affected by vegetation community types, phenology, and forest density. Previous long-term catchment-scale model studies have focused on changes in forest areas while ignoring the above factors. Since the 1980s, climate change caused by increases in atmospheric CO2 levels has enhanced forest growth. Moreover, amendments to forest management policies, including intermediate cuttings caused by economic factors, have yielded unprecedented changes in forest ecosystems. In this study, we designed a methodology and created a credible model using the Soil and Water Assessment Tool (SWAT) that can precisely reflect water balance variations caused by different ecosystem situations during long-term changes in forest density. We focused on the Yamato River catchment in Western Japan, which includes three planted forests and one primeval forest, each markedly different with respect to vegetation community composition and management policy. In the process, we examined the ratio of coniferous vegetation and broad-leaved vegetation in different forest areas, used remote sensing methods to quantify the maximum and minimum leaf area index (LAI) of each forest region over 40 years, and calibrated the model by comparing the LAI growth curve, evapotranspiration, and streamflow with observed data. Moreover, we separated the decadal canopy evaporation, transpiration, and soil evaporation from the SWAT output results. We found that (1) forest evapotranspiration has increased in recent decades because of the above reasons; (2) in young or well-managed forests, the forest water balance may have changed significantly with forest growth. For long-term studies, it is necessary to distinguish the growth characteristics of different forests during different periods, and a detailed definition of a mixed forest is required. The forest parameters and growth characteristics are critical for understanding forest ecosystems and cannot be ignored at catchment-scale.

210Pb dating to investigate the historical variations and identification of different sources of heavy metal pollution in sediments of the Pearl River Estuary, Southern China.

In this study, we investigated the historical variation, source identification, and distribution of heavy metal pollution in sediments of the Pearl River Estuary (PRE) using 210Pb dating. Our results suggest that the heavy metal concentrations were higher in the western part of the estuary. For all heavy metals, Cd was significantly enriched in the sediments. The Pearl River Delta (PRD) has experienced rapid economic development in the past 40 years, a decreasing trend in heavy metal fluxes after 2004 was identified, which suggests a reduction in heavy metal concentrations due to the removal of heavy polluting industries and the effective control of sewage discharge. A binary mixing model reveals that the contributions of anthropogenic Pb ranged from 45.4 to 64%. Based on lead isotopic ratios (206/207Pb and 208/206Pb), it was found that geologic materials and industrial pollution were the main sources of heavy metals in the PRE sediments.

Effects of environmental regulations on heavy metal pollution decline in core sediments from Manila Bay.

We investigated the high-resolution heavy metal pollution history of Manila Bay using heavy metal concentrations and Pb isotope ratios together with (210)Pb dating to find out the effects of environmental regulations after the 1990 s. Our results suggested that the rate of decline in heavy metal pollution increased dramatically from the end of the 1990 s due to stricter environmental regulations, Administrative Order No. 42, being enforced by the Philippines government. The presented data and methodology should form the basis for future monitoring, leading to pollution control, and to the generation of preventive measures at the pollution source for the maintenance of environmental quality in the coastal metropolitan city of Manila. Although this is the first report of a reduction in pollution in Asian developing country, our results suggest that we can expect to find similar signs of pollution decline in other parts of the world as well.

Erratum to "Effects of intensive urbanization on the intrusion of shallow groundwater into deep groundwater: examples from Bangkok and Jakarta".

Asian megacities have severe pollution problems in both coastal and urban areas. In addition, the groundwater potential has decreased and land subsidence has occurred because of intensive groundwater pumping in urban areas. To prevent the adverse effects of urbanization on groundwater quality, it is necessary to confirm the changes in groundwater flow and contaminant transport caused by urbanization. We examined the effects of urbanization on contaminant transport in groundwater. The research areas were located around Bangkok, Thailand, and Jakarta, Indonesia, cities with populations of approximately 8 and 12 million, respectively. Each metropolitan city is located on a river delta and is adjacent to a bay. We measured the water level and collected water samples at boreholes at multiple depths (100 to 200 m) in 2004 and 2006 in Bangkok and Jakarta, respectively. The current hydraulic potential is below sea level in both cities because of prior excess abstraction of groundwater. As a result, the direction of groundwater flow is now downward in the coastal area. The Cl- concentration and delta18O distributions in groundwater suggest that the decline in hydraulic potential has caused the intrusion of seawater and shallow groundwater into deep groundwater. Concentrations of Mn and NO3--N in groundwater suggest the intrusion of these contaminants from shallow to deep aquifers with downward groundwater flow and implies an accumulation of contaminants in deep aquifers. Therefore, it is important to recognize the possibility of future contaminant transport with the discharge of deep groundwater into the sea after the recovery of groundwater potential in the coastal areas.

Erratum to "Sources of nitrate and ammonium contamination in groundwater under developing Asian megacities".

The status of nitrate (NO3-), nitrite (NO2-) and ammonium (NH4 +) contamination in the water systems, and the mechanisms controlling their sources, pathways, and distributions were investigated for the Southeast Asian cities of Metro Manila, Bangkok, and Jakarta. GIS-based monitoring and dual isotope approach (nitrate delta15N and delta18O) suggested that human waste via severe sewer leakage was the major source of nutrient contaminants in Metro Manila and Jakarta urban areas. Furthermore, the characteristics of the nutrient contamination differed depending on the agricultural land use pattern in the suburban areas: high nitrate contamination was observed in Jakarta (dry fields), and relatively lower nutrients consisting mainly of ammonium were detected in Bangkok (paddy fields). The exponential increase in NO3--delta15N along with the NO3- reduction and clear delta18O/delta15N slopes of NO3- (approximately 0.5) indicated the occurrence of denitrification. An anoxic subsurface system associated with the natural geological setting (e.g., the old tidal plain at Bangkok) and artificial pavement coverage served to buffer NO3- contamination via active denitrification and reduced nitrification. Our results showed that NO3- and NH4+ contamination of the aquifers in Metro Manila, Bangkok, and Jakarta was not excessive, suggesting low risk of drinking groundwater to human health, at present. However, the increased nitrogen load and increased per capita gross domestic product (GDP) in these developing cities may increase this contamination in the very near future. Continuous monitoring and management of the groundwater system is needed to minimize groundwater pollution in these areas, and this information should be shared among adjacent countries with similar geographic and cultural settings.

Anthropogenic effects on the subsurface thermal and groundwater environments in Osaka, Japan and Bangkok, Thailand.

Anthropogenic effects in both Osaka and Bangkok were evaluated to compare the relationships between subsurface environment and the development stage of both cities. Subsurface thermal anomalies due to heat island effects were found in both cities. The Surface Warming Index (SWI), the departure depth from the steady geothermal gradient, was used as an indicator of the heat island effect. SWI increases (deeper) with the magnitude of heat island effect and the elapsed time starting from the surface warming. Distributions of subsurface thermal anomalies due to the heat island effect agreed well with the distribution of changes in air temperature due to the same process, which is described by the distribution of population density in both Osaka and Bangkok. Different time lags between groundwater depression and subsidence in the two cities was found. This is attributed to differences in hydrogeologic characters, such as porosity and hydraulic conductivity. We find that differences in subsurface degradations in Osaka and Bangkok, including subsurface thermal anomalies, groundwater depression, and land subsidence, depends on the difference of the development stage of urbanization and hydrogeological characters.

Human impacts on groundwater flow and contamination deduced by multiple isotopes in Seoul City, South Korea.

The influence of human activities on the flow system and contamination of groundwater were investigated in Seoul City, South Korea, one of the largest Asian cities, using a combination of isotopes (deltaD, T, delta15N, delta18O, delta34S, and 87Sr/86Sr). Eighteen representative groundwater and river water samples, which were collected over a wide area of the city, were compared with previously reported data. The distribution of stable isotopes (deltaD and delta18O) with groundwater potential data shows that recharged groundwater from either the surrounding mountainous area as well as the Han River and other surface streams discharged towards the northern-central part of the city, where a subway tunnel pumping station is located. It is suggested from T values (3.3 to 5.8 T.U.) that groundwater was recharged in the last 30 to 40 years. The delta34S and delta15N of SO4(2-) and NO3- data were efficiently used as indicators of contamination by human activities. These isotopes clarified that the contribution of anthropogenic contaminants i.e., industrial and household effluents, waste landfills, and fertilizers, are responsible for the enrichment by SO4(2-) (>30 ppm as SO4(2-)) and NO3- (>20 ppm as NO3-) of groundwater. The 87Sr/86Sr values of groundwater vary (0.71326 to 0.75058) in accordance with the host rocks of different origins. Mineral elements such as Ca are also suggested to be derived naturally from rocks. The groundwater under Seoul City is greatly affected by transportation of pollutants along the groundwater flow controlled by subway tunnel pumping, contributing to the degradation of water quality in urbanized areas.

Effects of intensive urbanization on the intrusion of shallow groundwater into deep groundwater: examples from Bangkok and Jakarta.

Asian megacities have severe pollution problems in both coastal and urban areas. In addition, the groundwater potential has decreased and land subsidence has occurred because of intensive groundwater pumping in urban areas. To prevent the adverse effects of urbanization on groundwater quality, it is necessary to confirm the changes in groundwater flow and contaminant transport caused by urbanization. We examined the effects of urbanization on contaminant transport in groundwater. The research areas were located around Bangkok, Thailand, and Jakarta, Indonesia, cities with populations of approximately 8 and 12 million, respectively. Each metropolitan city is located on a river delta and is adjacent to a bay. We measured the water level and collected water samples at boreholes at multiple depths (100 to 200 m) in 2004 and 2006 in Bangkok and Jakarta, respectively. The current hydraulic potential is below sea level in both cities because of prior excess abstraction of groundwater. As a result, the direction of groundwater flow is now downward in the coastal area. The Cl(-) concentration and delta(18)O distributions in groundwater suggest that the decline in hydraulic potential has caused the intrusion of seawater and shallow groundwater into deep groundwater. Concentrations of Mn and NO3(-)-N in groundwater suggest the intrusion of these contaminants from shallow to deep aquifers with downward groundwater flow and implies an accumulation of contaminants in deep aquifers. Therefore, it is important to recognize the possibility of future contaminant transport with the discharge of deep groundwater into the sea after the recovery of groundwater potential in the coastal areas.

Sources of nitrate and ammonium contamination in groundwater under developing Asian megacities.

The status of nitrate (NO(3)(-)), nitrite (NO(2)(-)) and ammonium (NH(4)(+)) contamination in the water systems, and the mechanisms controlling their sources, pathways, and distributions were investigated for the Southeast Asian cities of Metro Manila, Bangkok, and Jakarta. GIS-based monitoring and dual isotope approach (nitrate delta(15)N and delta(18)O) suggested that human waste via severe sewer leakage was the major source of nutrient contaminants in Metro Manila and Jakarta urban areas. Furthermore, the characteristics of the nutrient contamination differed depending on the agricultural land use pattern in the suburban areas: high nitrate contamination was observed in Jakarta (dry fields), and relatively lower nutrients consisting mainly of ammonium were detected in Bangkok (paddy fields). The exponential increase in NO(3)(-)-delta(15)N along with the NO(3)(-) reduction and clear delta(18)O/delta(15)N slopes of NO(3)(-) ( approximately 0.5) indicated the occurrence of denitrification. An anoxic subsurface system associated with the natural geological setting (e.g., the old tidal plain at Bangkok) and artificial pavement coverage served to buffer NO(3)(-) contamination via active denitrification and reduced nitrification. Our results showed that NO(3)(-) and NH(4)(+) contamination of the aquifers in Metro Manila, Bangkok, and Jakarta was not excessive, suggesting low risk of drinking groundwater to human health, at present. However, the increased nitrogen load and increased per capita gross domestic product (GDP) in these developing cities may increase this contamination in the very near future. Continuous monitoring and management of the groundwater system is needed to minimize groundwater pollution in these areas, and this information should be shared among adjacent countries with similar geographic and cultural settings.