Jun Shan

Nitrogen Removal Capacity of the River Network in a High Nitrogen Loading Region

Denitrification is the primary process that regulates the removal of bioavailable nitrogen (N) from aquatic ecosystems. Quantifying the capacity of N removal from aquatic systems can provide a scientific basis for establishing the relationship between N reduction and water quality objectives, quantifying pollution contributions from different sources, as well as recommending control measures. The Lake Taihu region in China has a dense river network and heavy N pollution; however, the capacity for permanent N removal by the river network is unknown. Here, we concurrently examined environmental factors and net N2 flux from sediments of two rivers in the Lake Taihu region between July 2012 and May 2013, using membrane inlet mass spectrometry, and then established a regression model incorporating the highly correlated factors to predict the N removal capacity of the river network in the region. To test the applicability of the regression model, 21 additional rivers surrounding Lake Taihu were sampled between July and December 2013. The results suggested that water nitrate concentrations are still the primary controlling factor for net denitrification even in this high N loading river network, probably due to multicollinearity of other relevant factors, and thus can be used to predict N removal from aquatic systems. Our established model accounted for 78% of the variability in the measured net N2 flux in these 21 rivers, and the total N removed through N2 production by the river network was estimated at 4 × 10(4) t yr(-1), accounting for about 43% of the total aquatic N load to the river system. Our results indicate that the average total N content in the river water discharged into Lake Taihu would be around 5.9 mg of N L(-1) in the current situation, far higher than the target concentration of 2 mg of N L(-1), given the total N load and the N removal capacity. Therefore, a much stronger effort is required to control the N pollution of the surface water in the region.

Dissimilatory Nitrate Reduction Processes in Typical Chinese Paddy Soils: Rates, Relative Contributions, and Influencing Factors

Using soil slurry-based (15)N tracer combined with N2/Ar technique, the potential rates of denitrification, anaerobic ammonium oxidation (anammox), and dissimilatory nitrate reduction to ammonium (DNRA), and their respective contributions to total nitrate reduction were investigated in 11 typical paddy soils across China. The measured rates of denitrification, anammox, and DNRA varied from 2.37 to 8.31 nmol N g(-1) h(-1), 0.15 to 0.77 nmol N g(-1) h(-1) and 0.03 to 0.54 nmol N g(-1) h(-1), respectively. The denitrification and anammox rates were significantly correlated with the soil organic carbon content, nitrate concentration, and the abundance of nosZ genes. The DNRA rates were significantly correlated with the soil C/N, extractable organic carbon (EOC)/NO3(-) ratio, and sulfate concentration. Denitrification was the dominant pathway (76.75-92.47%), and anammox (4.48-9.23%) and DNRA (0.54-17.63%) also contributed substantially to total nitrate reduction. The N loss or N conservation attributed to anammox and DNRA was 4.06-21.24 and 0.89-15.01 g N m(-2) y(-1), respectively. This study reports the first simultaneous investigation of the dissimilatory nitrate reduction processes in paddy soils, highlighting that anammox and DNRA play important roles in removing nitrate and should be considered when evaluating N transformation processes in paddy fields.

Nitrite behavior accounts for the nitrous oxide peaks following fertilization in a fluvo-aquic soil

It has been widely demonstrated—both in the field and the laboratory—that N fertilization stimulates peaks in nitrous oxide (N2O) emissions in agricultural soils. However, the mechanisms responsible for this phenomenon remain unclear. In this study, three aerobic incubation experiments were designed to: (1) evaluate the effects of urea and nitrification inhibitors (NIs) on inorganic N concentrations and N2O emissions; (2) establish the relationship between nitrite concentration and N2O emission by adding different amounts of nitrite to soil, and identify the contributions of abiotic processes to N2O production from nitrite by sterilization; and (3) explore the underlying reasons for nitrite accumulation by using 15N tracer methods. Compared with NI treatments, substantial nitrite accumulated in the UREA treatment, mainly attributed to the inhibitory effects of high ammonium from urea hydrolysis on transformation of 15N-nitrite to 15N-nitrate. N2O emission from soil was related to soil nitrite concentration, according to the Michaelis–Menten relationship (R2 = 0.998; P < 0.01). No significant N2O emission was observed in sterilized soil, indicating that N2O production was a microbial process with the probable dominance of nitrifier denitrification (ND). In conclusion, our results suggest that ammonium fertilizer stimulates nitrite accumulation by inhibiting nitrite transformation to nitrate, thus resulting in an increase in N2O emissions, while NIs reduce N2O emissions by suppressing nitrite formation.

Inhibitory effects of carbon nanotubes on the degradation of 14C-2,4-dichlorophenol in soil.

Concerns on the potential risks of engineered nanoparticles to the environment are increasing; however, little is known about the effects of carbon nanotubes (CNTs) on the environmental fate of hydrophobic organic pollutants in soil. We incubated radioactive labeled 2,4-dichlorophenol ((14)C-2,4-DCP) in a soil in the presence of various concentrations (0, 2, 20, and 2000 mg kg(-1) dry soil) of single-walled (SWCNTs) and multi-walled (MWCNTs) carbon nanotubes, and determined the mineralization, degradation, and residue distribution of 2,4-DCP in the soil. CNTs were added to the soil either after the spiking of (14)C-2,4-DCP or together with (14)C-2,4-DCP as a mixture. CNTs at the concentration of 2000 mg kg(-1) significantly (P<0.05) inhibited the mineralization of (14)C-2,4-DCP and induced a 2.3- to 3.9-fold increase in the amounts of the non-degraded (14)C-2,4-DCP in the soil after 90 d of incubation. Pre-adsorption of (14)C-2,4-DCP on CNTs showed stronger inhibitory effects on the degradation of (14)C-2,4-DCP, already significant with CNTs at 20 mg kg(-1). In general, SWCNTs had a higher effect on the degradation and residue distribution of 2,4-DCP in the soil than MWCNTs. The inhibitory effects are supposed to be owing to limited activities of soil endogenous microorganisms, potential toxicities of CNTs to the microorganisms, and reduced bioavailability of 2,4-DCP in the presence of CNTs, even though a desorption hysteresis of 2,4-DCP on CNTs was not observed. Our results indicate that CNTs have more significant impacts on the environmental fate of the hydrophobic pollutants entering soil together with CNTs via strong sorption than the pollutants already present in soil.

Degradation and bound-residue formation of nonylphenol in red soil and the effects of ammonium.

Fate of nonylphenol (NP) in soils and the effects of nitrogen fertilizers are unclear. Using (14)C-tracer, we studied the aerobic and anaerobic degradation of 4-NP111 in a paddy red soil amended without and with ammonium chloride. Under oxic conditions, 4-NP111 had a half-life of 16.1 ± 1.6 days and minor mineralization (3.84 ± 0.02%), forming no extractable metabolite but abundant bound residues (60.9 ± 1.7%, mostly bound to humin) after 49 days of incubation. The ammonium amendment (8 mmol/kg soil) significantly inhibited the degradation (half-life of 68.0 ± 7.7 days), mineralization (2.0 ± 1.1%), and bound-residue formation (23.7 ± 0.2%). Under anoxic conditions, 4-NP111 did not degrade during 49 days of incubation and the ammonium amendment (40 mmol/kg soil) did not affect its persistence. Our results demonstrate that bound-residue formation was a major mechanism for NP dissipation in the red soil under oxic conditions and that chemical nitrogen fertilizer at average field application rate may already considerably increase NP recalcitrance in agricultural soils.

Effects of the geophagous earthworm Metaphire guillelmi on sorption, mineralization, and bound-residue formation of 4-nonylphenol in an agricultural soil

Effects of earthworms on fate of nonylphenol (NP) are obscure. Using (14)C-4-NP111 as a representative, we studied the fate of 4-NP in an agricultural soil with or without the earthworm Metaphire guillelmi and in fresh cast of the earthworm. Sorption of 4-NP on the cast (Kd 1564) was significantly higher than on the parent soil (Kd 1474). Mineralization of 4-NP was significantly lower in the cast (13.2%) and the soil with earthworms (10.4%) than in the earthworm-free soil (16.0%). One nitro metabolite of 4-NP111 (2-nitro-4-NP111) was identified in the soil and cast, and the presence of the earthworm significantly decreased its amounts. The presence of earthworm also significantly decreased formation of bound residues of 4-NP in the soil. Our results demonstrate that earthworms could significantly change the fate of 4-NP, underlining that earthworm effects should be considered when evaluating behavior and risk of 4-NP in soil.

Effects of biochar and the geophagous earthworm Metaphire guillelmi on fate of 14C-catechol in an agricultural soil

Both biochar and earthworms can exert influence on behaviors of soil-borne monomeric phenols in soil; however, little was known about the combined effects of biochar and earthworm activities on fate of these chemicals in soil. Using (14)C-catechol as a representative, the mineralization, transformation and residue distribution of phenolic humus monomer in soil amended with different amounts of biochar (0%, 0.05%, 0.5%, and 5%) without/with the geophagous earthworm Metaphire guillelmi were investigated. The results showed biochar at amendment rate <0.5% did not affect (14)C-catechol mineralization, whereas 5% biochar amendment significantly inhibited the mineralization. Earthworms did not affect the mineralization of (14)C-catechol in soil amended with <0.5% biochar, but significantly enhanced the mineralization in 5% biochar amended soil when they were present in soil for 9 d. When earthworms were removed from the soil, the mineralization of (14)C-catechol was significantly lower than that of in earthworm-free soil indicating that (14)C-catecholic residues were stabilized during their passage through earthworm gut. The assimilation of (14)C by earthworms was low (1.2%), and was significantly enhanced by biochar amendment, which was attributed to the release of biochar-associated (14)C-catecholic residues during gut passage of earthworm.