ALBERT

Description: Hydrogeochemistry of 10 hot springs in the Kangding district was investigated by analyzing cation and anion concentrations in the spring water. The water samples were collected in the 5 days after the Lushan MS = 7.0 earthquake, which occurred on 20 April 2013. The spring waters are classified into seven chemical types based on their hydrochemical compositions. Compared with hydrochemical data before the Lushan earthquake, concentrations of Ca2+, HCO3- and total dissolved solid (TDS) in water samples from the Guanding, Erdaoqiao, Gonghe, Erhaoying, Tianwanhe and Caoke springs significantly increased, which may be the result of a greater increase in groundwater from carbonate rocks, and water–carbonate rock interactions, enhanced by the increment of CO2. Concentrations of Na+, Cl- and SO42- in water samples from the Guanding, Zheduotang, Xinxing and Gonghe springs decreased, indicating a dilution of shallow waters. Concentrations of Na+ and SO42- in water samples from the Erhaoying spring water increased, which may be attributed to water–granite interactions enhanced by H2S. The results indicated that hydrochemical components of spring water could be used as an effective indicator for earthquakes.

Description: This paper assesses the impacts of the Three Gorges Dam, the South–North Water Transfer Project and other water abstractions on the probability of long-duration salt intrusions into the Yangtze River estuary. Studies of intrusions of saltwater into estuaries are typically constrained by both the short duration of discharge records and the paucity of observations of discharge and salinity. Thus, studies of intrusions of saltwater into estuaries typically seek to identify the conditions under which these intrusions occur, using detailed observations for periods of 20–60 days. The paper therefore first demonstrates a method by which to identify the conditions under which intense intrusions of long-duration occur and then applies that method to analyse the effect of the three projects. The paper constructs a model of the relationship between salinity and discharge and then employs Monte Carlo simulation methods to reconstruct the probability of observing intrusions of differing intensities and durations in relation to discharge. The model predicts that the duration of intrusions with chlorinity ≥ 250 mg L−1 (or ≥ 400 or 500 mg L−1) increases as the number of consecutive days with discharge ≤ 12 000 m3 s−1 (or ≤ 8000 m3 s−1 increases. The model predicts that in 1950–2014, the number of consecutive days with chlorinity ≥ 250 mg L−1 averaged 21.34 yr−1; if the three projects operate according to their normal rules, that average would rise to 41.20 yr−1. For a randomly selected year of discharge history from the period 1950–2014, under normal operating rules for these projects the probability of an intrusion rises from 0.25 (for 30-day intrusions) or 0.05 (for 60-day intrusions) to 0.57 or 0.28, respectively.

Description: Studies of intrusions of salt water into estuaries are typically constrained by both the short duration of discharge records and the paucity of observations of discharge and salinity. Thus studies of intrusions of salt water into estuaries typically seek to identify the conditions under which intrusions occur, using detailed observations for periods of 20–60 days. This paper demonstrates a method by which to identify the conditions under which intense intrusions of long duration occur and applies that method to the Yangtze River estuary. The paper constructs a model of the relationship between salinity and discharge and then employs Monte Carlo simulation methods to reconstruct the probability of observing intrusions of differing intensities and durations in relation to discharge. The model predicts that the duration of intrusions with chlorinity ≥250 mg L−1 increases as the number of consecutive days with discharge ≤12 000 m3 s−1 increases; consecutive days of discharges ≤8000 m3 s−1 predict the duration of intrusions with chlorinity ≥400 or 500 mg L−1. In 26 of the 64 years analysed, the probability of an intrusion of at least 60 days at ≥250 mg L−1 is greater than 1 in 1000; in 17 years is greater than 1 in 100; and in ten years is greater than 1 in 10.

Description: Hydrogen peroxide (H2O2) and organic peroxides play important roles in the cycle of oxidants and the formation of secondary aerosols in the atmosphere. Recent field observations suggest that peroxyacetic acid (PAA, CH3C(O)OOH) is one of the most important organic peroxides in the atmosphere, whose budget is potentially related to the aerosols. Here we present the first laboratory measurements of the uptake coefficient of gaseous PAA and H2O2 onto the ambient fine particulate matter (PM2.5) as a function of relative humidity (RH) at 298 K. The results show that the PM2.5, which was collected in an urban area, can take up PAA and H2O2 at the uptake coefficient (γ) of 10−4, and both γPAA and γH2O2 increase with increasing RH. However, γPAA is more sensitive to the RH variation than is γH2O2, which indicates that the enhanced uptake of peroxide compounds on PM2.5 under humid conditions is dominated by chemical processes rather than dissolution. Considering that mineral dust is one of the main components of PM2.5, we also determined the uptake coefficients of gaseous PAA and H2O2 on authentic Asian Dust Storm (ADS) and Arizona Test Dust (ATD) particles. Compared to ambient PM2.5, ADS shows a similar γ value and RH dependence in its uptake coefficient for PAA and H2O2, while ATD gives a negative dependence on RH. The present study indicates that in addition to the mineral dust in PM2.5, other components (e.g., inorganic soluble salts) are also important to the uptake of peroxide compounds. When the heterogeneous reaction of PAA on PM2.5 is considered, its atmospheric lifetime is estimated to be 3.3 h on haze days and 7.6 h on non-haze days, values which agree well with the field observed result.

Description: Organic peroxides, important species in the atmosphere, will promote secondary organic aerosols (SOA) aging, affect HOx radicals cycling, and cause adverse health effects. However, the formation, gas-particle partitioning, and evolution of organic peroxides are extremely complicated and still unclear. In this study, we investigate in the laboratory the production and gas-particle partitioning of peroxides from the ozonolysis of α-pinene, which is one of the major biogenic volatile organic compounds in the atmosphere and is an important precursor for SOA at a global scale. We have determined the molar yields of hydrogen peroxide (H2O2), hydroxymethyl hydroperoxide (HMHP), peroxyformic acid (PFA), peroxyacetic acid (PAA) and total peroxides (TPO, including unknown peroxides) and the fraction of peroxides in SOA. Comparing the gas-phase and particle-phase peroxides, we find that gas-particle partitioning coefficients of PFA and PAA are 104 times higher than theoretical prediction, indicating that organic peroxides play a more important role in the SOA formation than expected previously. Here, we give the partitioning coefficients of TPO as (2–3) × 10-4 m3μg-1. Even so, more than 80 % of the peroxides formed in the reaction remain in the gas phase. Water does not affect the total amount of peroxides in either the gas or particle phase, but can change the distribution of gaseous peroxides. About 18 % gaseous peroxides undergo rapid heterogeneous decomposition on SOA particles in the presence of water vapor, resulting in the additional production of H2O2. This process can partially interpret the unexpected high H2O2 yield under wet conditions. Transformation of organic peroxides to H2O2 also saves OH in the atmosphere, helping to improve the understanding of OH cycling.

Description: The existence and importance of peroxyformic acid (PFA) in the atmosphere has been under controversy. We present here, for the first time, the observation data for PFA from four field measurements carried out in China. These data provided powerful evidence that PFA can stay in the atmosphere, typically in dozens of pptv level. The relationship between PFA and other detected peroxides was examined. The results showed that PFA had a strong positive correlation with its homolog, peroxyacetic acid, due to their similar sources and sinks. Through an evaluation of PFA production and removal rates, we proposed that the reactions between peroxyformyl radical (HC(O)O2) and formaldehyde or the hydroperoxyl radical (HO2) were likely to be the major source and degradation into formic acid (FA) was likely to be the major sink for PFA. Based on a box model evaluation, we proposed that the HC(O)O2 and PFA chemistry was a major source for FA under low NOx conditions. Furthermore, it is found that the impact of the HC(O)O2 and PFA chemistry on radical cycling was dependent on the yield of HC(O)O2 radical from HC(O) + O2 reaction. When this yield exceeded 50%, the HC(O)O2 and PFA chemistry should not be neglected for calculating the radical budget. To make clear the exact importance of HC(O)O2 and PFA chemistry in the atmosphere, further kinetic, field and modeling studies are required.

Description: Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle – an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understanding feedbacks in the climate system. We measured the oxygen and hydrogen isotope composition of water vapor from a very tall tower (185 m) in the Upper Midwest, United States to help diagnose the sources, transport, and fractionation of water vapor in the planetary boundary layer (PBL) over a 3-year period (2010 to 2012). These measurements represent the first set of annual water vapor isotope observations for the region. Models and cross wavelet analyses were used to assess the importance of Rayleigh, evapotranspiration (ET), and PBL entrainment processes on the isotope composition of water vapor. The vapor isotope composition at this tall tower site showed a very large seasonal amplitude (mean monthly δ18Ov ranged from −40.1 to −15.5 ‰ and δ2Hv ranged from −278.7 to −109.1 ‰) and followed the familiar Rayleigh distillation relation with water vapor mixing ratio at the annual time-scale. However, this relation was strongly modulated by ET and PBL entrainment processes at time-scales ranging from hours to several days. The wavelet coherence spectra indicate that the oxygen isotope ratio and the deuterium excess (dx) of water vapor are sensitive to synoptic and PBL processes. According to the phase of the coherence analyses, we show that ET often leads changes in dx, confirming that it is a potential tracer of regional ET. Isotope mixing models indicate that on average about 31 % of the growing season PBL water vapor is derived from regional ET. However, isoforcing calculations and mixing model analyses for high PBL water vapor mixing ratios events (〉 25 mmol mol−1) indicate that regional ET can account for 40 % to 60 % of the PBL water vapor. These estimates are in relatively good agreement with that derived from numerical weather model simulations. This relatively large fraction of ET-derived water vapor implies that ET has an important impact on the precipitation recycling ratio within the region. Based on multiple constraints, we estimate that the summer season recycling fraction is about 30 %, indicating a potentially important link with convective precipitation.

Description: Ecological models are effective tools for simulating the distribution of global carbon sources and sinks. However, these models often suffer from substantial biases due to inaccurate simulations of complex ecological processes. We introduce a set of scaling factors (parameters) to an ecological model on the basis of plant functional type (PFT) and latitudes. A global carbon assimilation system (GCAS-DOM) is developed by employing a dual optimization method (DOM) to invert the time-dependent ecological model parameter state and the net carbon flux state simultaneously. We use GCAS-DOM to estimate the global distribution of the CO2 flux on 1° × 1° grid cells for the period from 2001 to 2007. Results show that land and ocean absorb −3.63 ± 0.50 and −1.82 ± 0.16 Pg C yr−1, respectively. North America, Europe and China contribute −0.98 ± 0.15, −0.42 ± 0.08 and −0.20 ± 0.29 Pg C yr−1, respectively. The uncertainties in the flux after optimization by GCAS-DOM have been remarkably reduced by more than 60%. Through parameter optimization, GCAS-DOM can provide improved estimates of the carbon flux for each PFT. Coniferous forest (−0.97 ± 0.27 Pg C yr−1) is the largest contributor to the global carbon sink. Fluxes of once-dominant deciduous forest generated by the Boreal Ecosystems Productivity Simulator (BEPS) are reduced to −0.78 ± 0.23 Pg C yr−1, the third largest carbon sink.

Description: The protracted recovery of marine ecosystems following the Permian–Triassic mass extinction may have been caused, in part, by episodic environmental and climatic crises during the Early Triassic, among which the Smithian–Spathian boundary (SSB) event is conspicuous. Here, we investigate the SSB event in the Shitouzhai section, Guizhou Province, South China, using a combination of carbonate carbon (δ13Ccarb) and carbonate-associated sulfate sulfur isotopes (δ34SCAS), rare earth elements, and elemental paleoredox and paleoproductivity proxies. The SSB at Shitouzhai is characterized by a +4‰ shift in δ13Ccarb and a −10 to −15‰ shift in δ34SCAS, recording negative covariation that diverges from the positive δ13Ccarb−δ34SCAS covariation that characterizes most of the Early Triassic. This pattern is inferred to reflect an increase in organic carbon burial (e.g., due to elevated marine productivity) concurrently with the oxidation of isotopically light H2S, as the result of enhanced vertical advection of nutrient- and sulfide-rich deep waters to the ocean-surface layer. Enhanced upwelling was likely a response to climatic cooling and the reinvigoration of global-ocean overturning circulation at the SSB. Coeval decreases in chemical weathering intensity and detrital sediment flux at Shitouzhai are also consistent with climatic cooling. A decline in marine biodiversity was probably associated with the late Smithian thermal maximum (LSTM) rather than with the SSB per se. The SSB thus marked the termination of the extreme hothouse conditions of the Griesbachian–Smithian substages of the Early Triassic and is significant as a record of accompanying climatic, environmental, and biotic changes. The ultimate cause of the SSB event is uncertain but may have been related to a reduction in intrusive magmatic activity in the Siberian Traps large igneous province.

Description: A field experiment was designed to study the effects of nitrogen (N) source and urease inhibitor N-(n-butyl) thiophosphoric triamide (NBPT) or nitrification inhibitor dicyandiamide (DCD) on nitrous oxide (N2O) emission and N use efficiency (NUE) in a sandy loam soil. Six treatments including no N fertilizer (control), N fertilizer urea alone (U), urea plus NBPT (NBPT), urea plus DCD (DCD), urea plus NBPT and DCD (NBPT plus DCD) and nitrate-based fertilizer nitrophosphate (NP) were designed and implemented separately during the wheat growth period. Seasonal cumulative N2O emissions with urea alone amounted to 0.49 ± 0.12 kg N2O-N ha−1 and were significantly (P 〈 0.05) reduced to 0.28 ± 0.03, 0.31 ± 0.01 and 0.26 ± 0.01 kg N2O-N ha−1 by application of DCD, NBPT and NBPT plus DCD, respectively. Cumulative N2O emissions from NP were 0.28 ± 0.01 kg N2O-N ha−1. A single N2O flux peak was identified following basal fertilization, and DCD and/or NBPT inhibition effects mainly occurred during the peak emission period. The NP application significantly (P 〈 0.05) increased wheat yield by 12.3% and NUE from 28.8% (urea alone) to 35.9%, while urease and/or nitrification inhibitors showed a slight increase effect. Our results clearly indicated that the application of urea as basal fertilizer, but not as supplemental fertilizer, together with DCD and NBPT is an effective practice to reduce N2O emissions. The application of NP instead of urea would be an optimum agricultural strategy for reducing N2O emissions and increasing crop yield and NUE for wheat cultivation in soils of the North China Plain.