Photo-transformation of acetaminophen sensitized by fluoroquinolones in the presence of bromide.

Fluoroquinolones (FQs) are a class of antibiotics with emerging concern. This study investigated the photochemical properties of two representative FQs, i.e., norfloxacin (NORF) and ofloxacin (OFLO). Results showed that both FQs could sensitize the photo-transformation of acetaminophen under UV-A irradiation, during which excited triplet state (3FQ*) was the main active species. In the presence of 3 mM Br‾, the photolysis rate of acetaminophen increased by 56.3% and 113.5% in the solutions with 10 µM NORF and OFLO, respectively. Such an effect was ascribed to the generation of reactive bromine species (RBS), which was verified by 3,5-dimethyl-1H-pyrazole (DMPZ) probing approach. 3FQ* reacts with acetaminophen through one-electron transfer, producing radical intermediates which then couple to each other. Presence of Br‾ did not lead to the formation of brominated products but the same coupling products, which suggests that radical bromine species, rather than free bromine, were responsible for the accelerated acetaminophen transformation. According to the identified reaction products and assisted with the theoretical computation, the transformation pathways of acetaminophen under UV-A irradiation were proposed. The results reported herein suggest that sunlight-driven reactions of FQs and Br‾ may influence the transformation of coexisting pollutants in surface water environments.

Aquatic photolysis of 2,4-dichloro-6-nitrophenol-the toxic nitrated byproduct of 2,4-dichlorophenol.

2,4-Dichloro-6-nitrophenol (DCNP) is a toxic nitrated byproduct of 2,4-dichlorophenol (2,4-DCP) commonly found in agriculturally impacted waters (e.g., paddy waters). DCNP has both genotoxicity and developmental toxicity and can cause endocrine disrupting effects on aquatic species. Herein, we investigated the photolysis of DCNP under UV254 irradiation in aqueous solutions. Results show that the anionic form of DCNP (DCNP-) is more photoreactive than the neutral form (DCNP0) due to its higher molar absorption coefficient and quantum yield. The presence of Suwannee River natural organic matter (SRNOM) inhibits the direct photolysis of DCNP through light screening. A series of photoproducts were identified by solid phase extraction (SPE) and high resolution-mass spectrometry (HR-MS) analysis. The photolysis of DCNP generates several photoproducts, including photoreduction, photonucleophilic substitution, photoionization, and dimerization intermediates. The primary photochemical mechanisms include photoionization from the singlet state and heterolytic C-Cl bond splitting in the triplet state. This contribution may shed some light on the photochemical transformation and fate of DCNP in UV-based engineering systems or natural sunlit surface waters.

Transformation of bromide and formation of brominated disinfection byproducts in peracetic acid oxidation of phenol.

Peracetic acid (PAA) has attracted increasing attention in wastewater treatment as a disinfectant. However, the transformation of bromide (Br-) during PAA oxidation of bromide-containing wastewater has not been fully explored. This study showed that Br- could be oxidized by PAA to free bromine which reacted with phenol to form organic bromine. At pH 7.0, more than 35.2% inorganic Br- was converted to organic bromines in 4 h. At acidic conditions, the conversion ratio was even higher, reaching 69.9% at pH 2.8. Most of the organic bromines were presented as bromophenols (i.e., 2-bromophenol, 4-bromophenol, and 2,4-dibromophenol), while regulated brominated disinfection byproducts (Br-DBPs, i.e., bromoform and bromoacetic acids) only accounted for a tiny fraction of total organic bromine. Similar results were observed when PAA was applied to natural organic matter (NOM) or wastewater in presence of Br-. The organic bromine yield reached 56.6 µM in the solution containing 0.1 mM Br- and 2 mg/L NOM initially. Among them, only 1.00 µM bromoform and 0.16 µM dibromoacetic acid were found. Similarly, regulated Br-DBPs only accounted for 28.3% of the organic bromine in a real wastewater effluent treated with PAA. All these data show that monitoring regulated DBPs cannot fully indicate the potential environmental risk of the application of PAA to wastewater.

Nitrite-mediated photodegradation of sulfonamides and formation of nitrated products.

In this study, we systematically investigated the indirect photolysis of five SAs, i.e., sulfamethazine (SMZ), sulfamethoxazole (SMX), sulfathiazole (STZ), sulfapyridine (SPD), and sulfamethizole (SMT), under UV-A irradiation (365 nm) and mediated by nitrite (NO2‾) at environmentally relevant concentrations (0.005-0.1 mM). The SAs that are resistant to direct photolysis can be effectively removed in UV/NO2‾ system. SAs with a six-membered heterocyclic ring (i.e., SMZ and SPD) were degraded more quickly than those with a five-membered heterocyclic ring (i.e., SMX, STZ and SMT). The pseudo-first-order rate constants (k) at nitrite concentration of 0.1 mM followed the order of kSPD (0.0265 min-1) > kSMZ (0.0245 min-1) > kSMX (0.0184 min-1) > kSTZ (0.0176 min-1) > kSMT (0.0154 min-1). A kinetic model was developed and the contributions of direct UV photolysis, OH, and RNS to SAs degradation in UV/NO2‾ system were calculated. At NO2‾ concentration of 0.1 mM, the contributions of OH and RNS for SAs removal were 29.17-46.53% and 52.33-63.28%, respectively. Main transformation pathways including hydroxylation and nitration were proposed, based on liquid chromatography mass spectrometry analysis of the degradation products and density functional theory calculation. However, Smile-type rearrangement which generated a SO2-extrusion product was only observed in the degradation of SAs with a six-membered ring, which explains their higher degradation rate than those with a five-membered ring. The presence of natural organic matter (NOM) decreased the formation of nitrated products. Overall, these results will be helpful to understand the fate and the potential ecological risks of SAs in sunlit aquatic environments.

The reduction effects of riparian reforestation on runoff and nutrient export based on AnnAGNPS model in a small typical watershed, China.

The continuous deterioration of the aquatic environment in rivers and streams is increasingly causing social and political tensions. To alleviate aquatic environmental problems, especially for the nonpoint source pollution, establishment of riparian forest buffers has been demonstrated as an effective control measure. However, few comprehensive studies of the reduction effects of riparian reforestation on the aquatic environment have been performed, particularly in identifying the suitable widths of reforestation projects. In this paper, the Annualized Agricultural Non-Point Source (AnnAGNPS) model was used to simulate the reduction effects of riparian reforestation on runoff and nutrient loads in Wucun watershed, China. The results showed that 20-m, 40-m, and 60-m widths of riparian buffer reforestation had significant effects on the yearly loads of total nitrogen (TN) and total phosphorus (TP), with reduced rates of 23.21 to 56.2% and 18.16 to 52.14%, respectively. The reduction effect on annual runoff varied from 2.8 to 5.4%. Furthermore, the reduction effect of nutrients performed best during the transition period, while the best runoff reduction was found during the dry period. These distinct reductions indicated that the implementation of riparian forest buffers was capable of reducing the risk and frequency of flooding and eutrophication, especially during the wet and transition periods. Additionally, the 20-m width of riparian buffer reforestation achieved the highest reduction efficiency for runoff, and the 40-m width was the most suitable reforested riparian buffer width for TN and TP. Therefore, 40 m may be the optimum buffer width for the implementation of riparian reforestation in the Wucun watershed. These research results provided scientific information on selecting the optimum buffer width for aquatic environmental regulators and managers as the reduction effects of different widths of riparian buffers on runoff and nutrients were different when considering buffer reforestation.

Chlorination and chloramination of benzophenone-3 and benzophenone-4 UV filters.

The objective of this research was to explore the fundamental reactions between chlorine/chloramine and 2-hydroxyl-4-methoxyl benzophenone (BP3)/2-hydroxyl-4-methoxyl benzophenone-sulfonic acid (BP4), which were the most common reactions in benzophenone-type UV filters during drinking water treatment processes. Both BP3 and BP4 could react with free chlorine and chloramine, with reactions following pseudo-first-order kinetics in excess of chlorine (HClO) and chloramine (NH2Cl). Generally, chlorination was more rapid than chloramination. BP4 was less reactive than BP3 toward both chlorine and chloramine, due to the presence of an electron-accepting sulfonate group. Therefore, BP3 had a significantly higher disinfection by-products (DBP) formation potential than BP4. Chlorination of BP3 and BP4 generated remarkably higher levels of DBPs than chloramination, with high pH conditions facilitating the formation of chloroform but inhibiting the formation of haloacetic acid (HAAs). Comparison of the reaction behavior of two different BP-type UV filters, i.e., BP3 and BP4, revealed that certain functional groups significantly affected the reactivity of BP-type UV filters in chlorination and chloramination processes. This contribution may provide new insights into the reaction behavior of UV filters during drinking water disinfection process using chlorine and/or chloramine as disinfectant, and provide guidelines for drinking water safety management.

Transformation of antimicrobial agent sulfamethazine by peroxymonosulfate: Radical vs. nonradical mechanisms.

Peroxymonosulfate (PMS) is increasingly used as an oxidant for in situ remediation of organic contaminants in soil and groundwater. In this study we demonstrated that sulfamethazine (SMZ) could be transformed by PMS in the absence of any activators. Such transformation was ascribed to the oxidation by PMS per se, rather than free radicals (SO4- or HO), superoxide (O2-), or singlet oxygen (1O2). The aniline moiety of SMZ molecule was the reactive site for PMS oxidation, leading to the formation of nitrated products. This nitration pathway in fact played a significant role in the removal of SMZ in activated PMS oxidation processes. For instance, it contributed 26% of the total SMZ transformation, while SO4- contributed the other 74% during the removal of SMZ, in Co(II)/PMS oxidation process with initial PMS and Co(II) concentrations of 1.0 mM and 0.1 µM, respectively. Similar nitration reaction also occurred to other sulfonamide antibiotics bearing an aniline moiety upon the reaction with PMS. Since nitrated sulfonamide antibiotics appear more persistent than the parent compounds and may cause other environmental problems, such a pathway should not be desired. Therefore, PMS might not be an ideal oxidant for the treatment of sulfonamide antibiotics and other compounds having aniline moieties, especially in subsurface remediation practices where efficient activation of PMS represents a major challenge.

Comparative study of the formation of brominated disinfection byproducts in UV/persulfate and UV/H2O2 oxidation processes in the presence of bromide.

The objective of this research was to compare the transformation of Br- and formation of brominated byproducts in UV/persulfate (PS) and UV/H2O2 processes. It was revealed that Br- was efficiently transformed to free bromine which reacted with humic acid (HA) or dihydroxybenzoic acid resulting in the formation of brominated byproducts such as bromoacetic acids (BAAs) in UV/PS system. In contrast, no free bromine and brominated byproducts could be detected in UV/H2O2 system, although the oxidization of Br- was evident. We presumed that the oxidation of Br- by hydroxyl radicals led to the formation of bromine radicals. However, the bromine radical species could be immediately reduced back to Br- by H2O2 before coupling to each other to form free bromine, which explains the undetection of free bromine and BAAs in UV/H2O2. In addition to free bromine, we found that the phenolic functionalities in HA molecules, which served as the principal reactive sites for free chlorine attack, could be in situ generated when HA was exposed to free radicals. This study demonstrates that UV/H2O2 is more suitable than UV/PS for the treatment of environmental matrices containing Br-. Graphical abstract Graphical abstract.

Transformation of iodide and formation of iodinated by-products in heat activated persulfate oxidation process.

Formation of halogenated disinfection by-products (DBPs) in sulfate radical-based advanced oxidation processes (SR-AOPs) have attracted considerable concerns recently. Previous studies have focused on the formation of chlorinated and brominated DBPs. This research examined the transformation of I- in heat activated PS oxidation process. Phenol was employed as a model compound to mimic the reactivity of dissolved natural organic matter (NOM) toward halogenation. It was found that I- was transformed to free iodine which attacked phenol subsequently leading to iodinated DBPs such as iodoform and iodoacetic acids. Iodophenols were detected as the intermediates during the formation of the iodoform and triiodoacetic acid (TIAA). However, diiodoacetic acid (DIAA) was formed almost concomitantly with iodophenols. In addition, the yield of DIAA was significantly higher than that of TIAA, which is distinct from conventional halogenation process. Both the facts suggest that different pathway might be involved during DIAA formation in SR-AOPs. Temperature and persulfate dose were the key factors governing the transformation process. The iodinated by-products can be further degraded by excessive SO4- and transformed to iodate. This study elucidated the transformation pathway of I- in SR-AOPs, which should be taken into consideration when persulfate was applied in environmental matrices containing iodine.

Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A: Kinetics, reaction pathways, and formation of brominated by-products.

Degradation of tetrabromobisphenol A (TBBPA), a flame retardant widely spread in the environment, in Co(II) catalyzed peroxymonosulfate (PMS) oxidation process was systematically explored. The second-order-rate constant for reaction of sulfate radical (SO4(-)) with TBBPA was determined to be 5.27×10(10)M(-1)s(-1). Apparently, degradation of TBBPA showed first-order kinetics to the concentrations of both Co(II) and PMS. The presence of humic acid (HA) and bicarbonate inhibited TBBPA degradation, most likely due to their competition for SO4(-). Degradation of TBBPA was initiated by an electron abstraction from one of the phenolic rings. Detailed transformation pathways were proposed, including ß-scission of isopropyl bridge, phenolic ring oxidation, debromination and coupling reactions. Further oxidative degradation of intermediates in Co(II)/PMS process yielded brominated disinfection by-products (Br-DBPs) such as bromoform and brominated acetic acids. Evolution profile of Br-DBPs showed an initially increasing and then decreasing pattern with maximum concentrations occurring around 6-10h. The presence of HA enhanced the formation of Br-DBPs significantly. These findings reveal potentially important, but previously unrecognized, formation of Br-DBPs during sulfate radical-based oxidation of bromide-containing organic compounds that may pose toxicological risks to human health.

A comparison of methane emissions following rice paddies conversion to crab-fish farming wetlands in southeast China.

Rice paddies and aquaculture wetlands are typical agricultural wetlands that constitute one of the important sources of atmospheric methane (CH4). Traditional transplanted rice paddies have been experiencing conversion to pond aquaculture wetlands for pursuing higher economic benefits over the past decades in southeast China. A parallel field experiment was carried out to compare CH4 emissions from a transplanted rice paddy and its converted crab-fish farming wetland in southeast China. Over the rice-growing season, CH4 fluxes averaged 1.86 mg m(-2) h(-1) from rice paddies, and 1.14 and 0.50 mg m(-2) h(-1) for the treatments with or without aquatic vegetation present in the crab-fish farming wetlands, respectively. When averaged across the treatments, seasonal CH4 emissions from crab-fish framing wetlands were 52% lower than those from rice paddies. The CH4 fluxes were negatively related to water dissolved oxygen (DO) concentration but positively related to soil/sediment dissolved organic carbon (DOC) content in crab-fish farming wetlands. Dependence of CH4 fluxes on DO or DOC was intensified by the aquatic vegetation presence. By extrapolating the present CH4 emission rate with the current rice paddy-converted aquaculture cultivation area, the seasonal CH4 emissions from inland aquaculture wetlands during the critical farming stage (20 June to 18 October) were estimated to be 33.6 Gg ha(-1) in southeast China in 2012. Rice paddies conversion to crab-fish farming wetlands might have reduced CH4 emissions by 22-54% in mainland China. Results of this study suggest that the conversion of transplanted rice paddies to crab-fish aquaculture wetlands for higher economic benefits would also lead to a lower ecosystem CH4 release rate.

Root aeration improves growth and nitrogen accumulation in rice seedlings under low nitrogen.

In wetland soils, changes in oxygen (O2) level in the rhizosphere are believed to influence the behaviour of nutrients and their usage by plants. However, the effect of aeration on nitrogen (N) acquisition under different N supply conditions remains largely unknown. In this study, the rice cultivars Yangdao 6 (YD6, with higher root aerenchyma abundance) and Nongken 57 (NK57, with lower root aerenchyma abundance) were used to evaluate the effects of aeration on rice growth and N accumulation. Our results showed that the number of adventitious roots and the root surface area increased significantly, and ethylene production and aerenchyma formation decreased in both cultivars after external aeration (EA). Five N treatments, including no N (-N), 0.125 mM NH4NO3 (LN), 1.25 mM Ca(NO3)2 (NO3-N), 1.25 mM (NH4)2SO4 (NH4-N) and 1.25 mM NH4NO3 (N/N), were applied to YD6 and NK57 for 2 days under internal aeration or EA conditions. External aeration increased the root biomass in both cultivars and the shoot biomass in NK57 by 18-50 %. The total N concentrations in roots of YD6 grown under -N and LN and of NK57 grown under NO3-N were increased by EA. Expression of OsPAD4, one of four putative genes regulating aerenchyma formation, showed a similar pattern alongside changes in the ethylene level in the EA-treated rice irrespective of the N treatments. Furthermore, expression of the high-affinity nitrate transporter gene OsNRT2.1 was increased by EA under -N, LN and NO3-N conditions. Our data provide evidence of an interaction between O2 and the supply of N in ethylene production, aerenchyma formation and N nutrition through modification of the expression of OsPAD4 and OsNRT2.1.

Kinetic and mechanistic investigations of the degradation of sulfamethazine in heat-activated persulfate oxidation process.

Sulfamethazine (SMZ) is widely used in livestock feeding and aquaculture as an antibiotic agent and growth promoter. Widespread occurrence of SMZ in surface water, groundwater, soil and sediment has been reported. In this study, degradation of SMZ by heat-activated persulfate (PS) oxidation was investigated in aqueous solution. Experimental results demonstrated that SMZ degradation followed pseudo-first-order reaction kinetics. The pseudo-first-order rate constant (kobs) was increased markedly with increasing concentration of PS and temperature. Radical scavenging tests revealed that the predominant oxidizing species was SO4·(-) with HO playing a less important role. Aniline moiety in SMZ molecule was confirmed to be the reactive site for SO4·(-) attack by comparison with substructural analogs. Nontarget natural water constituents affected SMZ removal significantly, e.g., Cl(-) and HCO3(-) improved the degradation while fulvic acid reduced it. Reaction products were enriched by solid phase extraction (SPE) and analyzed by liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-MS/MS). 6 products derived from sulfonamide S--N bond cleavage, aniline moiety oxidation and Smiles-type rearrangement were identified, and transformation pathways of SMZ oxidation were proposed. Results reveal that heat-activated PS oxidation could be an efficient approach for remediation of water contaminated by SMZ and related sulfonamides.

Simulation of runoff and nutrient export from a typical small watershed in China using the Hydrological Simulation Program-Fortran.

The Hydrological Simulation Program-Fortran (HSPF), which is a hydrological and water-quality computer model that was developed by the United States Environmental Protection Agency, was employed to simulate runoff and nutrient export from a typical small watershed in a hilly eastern monsoon region of China. First, a parameter sensitivity analysis was performed to assess how changes in the model parameters affect runoff and nutrient export. Next, the model was calibrated and validated using measured runoff and nutrient concentration data. The Nash-Sutcliffe efficiency (E NS ) values of the yearly runoff were 0.87 and 0.69 for the calibration and validation periods, respectively. For storms runoff events, the E NS values were 0.93 for the calibration period and 0.47 for the validation period. Antecedent precipitation and soil moisture conditions can affect the simulation accuracy of storm event flow. The E NS values for the total nitrogen (TN) export were 0.58 for the calibration period and 0.51 for the validation period. In addition, the correlation coefficients between the observed and simulated TN concentrations were 0.84 for the calibration period and 0.74 for the validation period. For phosphorus export, the E NS values were 0.89 for the calibration period and 0.88 for the validation period. In addition, the correlation coefficients between the observed and simulated orthophosphate concentrations were 0.96 and 0.94 for the calibration and validation periods, respectively. The nutrient simulation results are generally satisfactory even though the parameter-lumped HSPF model cannot represent the effects of the spatial pattern of land cover on nutrient export. The model parameters obtained in this study could serve as reference values for applying the model to similar regions. In addition, HSPF can properly describe the characteristics of water quantity and quality processes in this area. After adjustment, calibration, and validation of the parameters, the HSPF model is suitable for hydrological and water-quality simulations in watershed planning and management and for designing best management practices.

Transformation of sulfonylurea herbicides in simulated drinking water treatment processes.

Sulfonylurea herbicides (SUs) were detected in natural waters and could be potentially exposed to human beings via portable use. Thus, the removal of five representative SUs in simulated water treatment processes including coagulation, activated carbon adsorption, and chlorination disinfection was systematically investigated. Results showed that coagulation had little effect on the removal of the herbicides with the average removal less than 10 %. Powder-activated carbon adsorption was apparently more effective with removal rates of 50 ~ 70 %. SUs were also partially removed in chlorination process. A complete removal was achieved when the three treatments were performed in series. However, it was found that parts of the SUs were transformed into certain stable products with triazine/pyrimidine structures which might be of potential health risks in chlorination process. Thus, current drinking water treatment processes are not likely to provide sufficient protection for human population from exposure to SUs.

Bacterial diversity losses: A potential extracellular driving mechanism involving the molecular ecological function of hydrophobic polycyclic aromatic hydrocarbons.

The DNA transformation is vital to the horizontal gene transfer (HGT). The low-efficiency transformation of bare plasmid exposed to hydrophobic polycyclic aromatic hydrocarbons (PAHs) decreases the gene transfer level, and is possibly related to the loss of bacterial diversity at present. PAHs have great affinity for bare DNA through dispersion force and π-π overlap between PAHs and bases. These noncovalent interactions between PAHs and bases reduced the transformational efficiency of plasmid into bacterial recipients. Meanwhile these low-efficiency transformations for plasmid are controlled by the ions like Ca2+ in environment, in turn, presence of 0.5 mmol L-1 Ca2+ recovered the efficiency from 3.2 (phenanthrene), 3.5 (pyrene) to about 4.45 and 4.75, respectively. The combination of Ca2+ with the -POO-- groups in DNA forms strong electrovalent bonds, weakening the molecular effect of DNA on PAHs and in turn promoting the gene transfer exposed to PAHs.

Insights into complexation of dissolved organic matter and Al(III) and nanominerals formation in soils under contrasting fertilizations using two-dimensional correlation spectroscopy and high resolution-transmission electron microscopy techniques.

Understanding the organomineral associations in soils is of great importance. Using two-dimensional correlation spectroscopy (2DCOS) and high resolution-transmission electron microscopy (HRTEM) techniques, this study compared the binding characteristics of organic ligands to Al(III) in dissolved organic matter (DOM) from soils under short-term (3-years) and long-term (22-years) fertilizations. Three fertilization treatments were examined: (i) no fertilization (Control), (ii) chemical nitrogen, phosphorus and potassium (NPK), and (iii) NPK plus swine manure (NPKM). Soil spectra detected by the 2DCOS Fourier transform infrared (FTIR) spectroscopy showed that fertilization modified the binding characteristics of organic ligands to Al(III) in soil DOM at both short- and long- term location sites. The CH deformations in aliphatic groups played an important role in binding to Al(III) but with minor differences among the Control, NPK and NPKM at the short-term site. While at the long-term site both C-O stretching of polysaccharides or polysaccharide-like substances and aliphatic O-H were bound to Al(III) under the Control, whereas only aliphatic O-H, and only polysaccharides and silicates, were bound to Al(III) under NPK and NPKM, respectively. Images from HRTEM demonstrated that crystalline nanominerals, composed of Fe and O, were predominant in soil DOM under NPK, while amorphous nanominerals, predominant in Al, Si, and O, were dominant in soil DOM under Control and NPKM. In conclusion, fertilization strategies, especially under long-term, could affect the binding of organic ligands to Al(III) in soil DOM, which resulted in alterations in the turnover, reactivity, and bioavailability of soil organic matter. Our results demonstrated that the FTIR-2DCOS combined with HRTEM techniques could enhance our understanding in the binding characteristics of DOM to Al(III) and the resulted nanominerals in soils.

[Impact of different levels of nitrogen fertilizer on N2O emission from different soils].

To investigate the effect of different urea incorporation amount in different soils on N2O emission, a pot experiment was carried in 2002-2003. Four treatments were designed as the control (without urea incorporation); low N fertilizer level (334 kg/hm2); middle N fertilizer level (670 kg/hm); high N fertilizer level (1004 kg/hm2). In rice growing season, compared to control, the increment of N2O emission accumulation flux of each soil has no obviously differences among three N fertilizer levels. Contrarily, in wheat-planted soils, there are remarkably differences among three N fertilizer levels. Without urea incorporation, there are no differences among N2O accumulation emission flux of three soils. During the rice growing season, N2O accumulation emission flux of F soil (jiangsu province, lishui), G soil (jiangsu province, lianshui) and H soil (jiangsu province, agriculture academy) are 168, 127 and 146 mg/m2, respectively. N2O accumulation emission flux of F soil, G soil and H soil is 134, 124 and 168 mg/m2, respectively, during wheat growing season. Incorporation of urea into different soils yielded different influence on N2O emission. For example, at middle-N fertilizer, N2O accumulation emission flux from F soil, G soil and H soil is 976, 744 and 626 mg/m2, respectively. During rice-wheat rotation period, significance differences exists among N2O emission factors of three soils, with the value of (1.1 +/- 0.23)%, (0.75 +/- 0.17%) and (1.01 +/- 0.11)%. Furthermore, under the high N fertilizer level, N2O emission factors of three soils had no significantly difference (p = 0.3); while, the N2O emission factors existed difference among three soils under the low and middle N fertilizer level (F = 6.25, p = 0.01).

[Impact of different levels of nitrogen fertilizer on CH4 emission from different paddy soils].

To investigate the effect of different urea incorporation amount in different soils on CH4 emission, a pot experiment was carried in 2002. Four treatments were designed as the control (without urea incorporation); low N fertilizer level (0.64 g urea/pot); middle N fertilizer level (1.28 g urea/pot); high N fertilizer level (1.93 g urea/pot). During rice growing season, incorporation of urea into different soils yielded different influence on CH4 emission. Without urea incorporation, significance differences existed among CH4 emission flux of three soils, with the values of 6.7 g/m2, 12.6 g/m2 and 8.3 g/m2, respectively. Incorporation of urea reduced considerably CH4 emission of three soils. A further investigation indicate that CH4 emission of three soils largely decreased and three soils NH4(+)-N content obviously increased from low N fertilizer level to middle N fertilizer level. It concluded that soil NH4(+)-N content is a key influence factor on CH4 emission after incorporation of urea into soils. From middle N level to high N level, CH4 emision of soil G (Lianshui, Jiangsu) and H (Jiangsu Academy of agricultural sciences) reduced, while CH4 emission of soil F (Lishui, Jiangsu) had no obvious significance with the value of 3.0 g/m2 and 3.4 g/m2.

[Methane emission from rice paddy soils as influenced by soil physicochemical properties].

To identify the key soil parameters influencing methane emission from rice paddies, and to quantitatively describe the relationship of methane emission with the soil properties, an outdoor pot experiment with a total of 18 paddy soils sampled from different regions in Jiangsu province was conducted in Nanjing Agricultural University during 2000 rice growing season. Seasonal average rate of CH4 emission for all the 18 soils was 6.42 +/- 2.70 mg.(m2.h)-1, ranging from 1.96 to 11.06 mg.(m2.h)-1, approximately a 5.6-fold difference between the maximum and the minimum. Correlation analysis indicated that the seasonal average of CH4 emission was positively dependent on soil sand content (r = 0.528, p = 0.024) and negatively on soil clay content (r = -0.484, p = 0.042). Negative correlation of CH4 emission against soil total nitrogen (r = -0.449, p = 0.062), available nitrogen (r = -0.611, p = 0.007) and NH4(+)-N(r = -0.649, p = 0.004) was also observed. Copper content of soils has a significant negative impact on CH4 emission. The correlation coefficient (r) of CH4 emission against soil available copper and with total copper was -0.594 (p = 0.009) and -0.547 (p = 0.019), respectively. No clear relationship existed between CH4 emission and soil carbon content. A further investigation suggests that the seasonal average rate of CH4 emission can be quantitatively determined by a linear combination of soil available copper, total manganese, and a ratio of available to total iron (R2 = 0.755, p = 0.0001).