贵州百花湖分层晚期有机质降解过程与溶解N2O循环

百花湖是一个具有季节性分层的富营养小型湖泊,在秋季湖水倒转期经常发生水质恶化事件,碳氮循环出现异常。文章研究特选择在秋初,湖泊分层开始消失时,测定了湖水中不同深度的N₂O,CH₄,CO₂,有机和无机碳同位素以及其他化学参数变化。结果发现:采样时百花湖在约6m和16m深度附近出现了两个温度不连续层(SDL和PDL),并影响到有机颗粒的沉降和分解。相对而言,有较多的有机质在这两个层内发生降解,但降解的途径有所不同,上部主要是有氧降解,下部则主要是无氧降解过程。N₂O的产生和消耗与有机质的降解过程完全对应:PDL层以上,ΔN₂O与AOU的线性关系反映了N₂O主要形成于硝化作用;PDL层以下反硝化作用导致N₂O严重不饱和;PDL内位于硝化作用和反硝化作用过渡带的N₂O峰,显然是硝化与反硝化联合作用的结果。PDL层内较大的CH₄浓度变化梯度,说明嗜甲烷细菌可能通过氧化NH+4贡献了部分N₂O。百花湖秋、冬季表层湖水N₂O都是过饱和的,都是大气N₂O的源,依据分子扩散模型计算湖泊N₂O的释放通量在12～14μmol/m·day之间,秋、冬季没有明显的差别。秋季底层湖水的反硝化作用是湖泊N₂O的汇,其消耗通量与表层的释放通量基本相当。     

Direct Current Plasma Emission Spectrometric Determination of Major, Minor and Trace Elements in Microwave Oven Acid Leachates of Powdered Whole Coal Samples

Major concentrations of Al₂O₃, Fe₂O₃, MgO, CaO, Na₂O and K₂O, minor levels of TiO₂, P₂O₅ and thirty petrologically, geochemically and environmentally significant trace elements have been determined in microwave oven acid leachates of whole powdered coal samples by direct current plasma‐atomic emission spectrometry (DCP‐AES). A single sample preparation procedure was suitable for all the determinations with no additional dilution step for major elements solution. Dried samples (0.5 g) were treated in low‐pressure PFA digestion vessels with HF/HCl/HNO₃/HClO₄ acids to quantitatively extract the analytes from the bulk material, while leaving the major part of organic matrix as a residue. The major constituents of geological samples, in particular the easily ionised elements (EIEs) such as alkali and alkaline earths, may complicate the instrumental determinations in DCP‐AES because of differential enhancements of elemental emission intensities and stray light interferences. Taking account of these factors, the coal matrix is considered to have very low major oxide totals as compared to many other common geo‐environmental and related materials (rocks, sediments, soil, ashes etc.). The sample size employed here, while yielding a relatively concentrated solution to cover a wide range of elemental determinations, provided a sample matrix that significantly diminished interferences for DCP measurements. The need for closely matching the unknowns and calibrators was eliminated except for overall acidity and an excess quantity of caesium for EIE buffering. Calibration of the spectrometer was accomplished by simple aqueous single element solutions as high concentration calibrators in addition to a reagent blank as a low concentration calibrator. Two point working curves were established to allow for the maximum concentrations of each element expected in the unknowns. The precision of determinations under routine conditions as well as the reproducibility of the leaching and precision of instrumental measurements have been evaluated. Relative standard deviations (RSD) were of 1–2% for those elements whose concentrations in solid samples were well above the limits of quantification. Method detection limits in the buffered solutions were also evaluated. To evaluate the accuracy of the microwave oven‐DCP method a suite of eight certified coal reference materials of differing rank, were analysed with good agreement with the certified and/or available published data. Results are presented for the uncertified major oxides in the AR series reference materials.     

Mercury and methylmercury biogeochemistry in a thawing permafrost wetland complex,Northwest Territories,Canada

In arctic and sub‐arctic environments, mercury (Hg), more specifically toxic methylmercury (MeHg), is of growing concern to local communities because of its accumulation in fish. In these regions, there is particular interest in the potential mobilization of atmospherically deposited Hg sequestered in permafrost that is thawing at unprecedented rates. Permafrost thaw and the resulting ground surface subsidence transforms forested peat plateaus into treeless and permafrost‐free thermokarst wetlands where inorganic Hg released from the thawed permafrost and draining from the surrounding peat plateaus may be transformed to MeHg. This study begins to characterize the spatial distribution of MeHg in a peat plateau–thermokarst wetland complex, a feature that prevails throughout the wetland‐dominated southern margin of thawing discontinuous permafrost in Canada's Northwest Territories. We measured pore water total Hg, MeHg, dissolved organic matter characteristics and general water chemistry parameters to evaluate the role of permafrost thaw on the pattern of water chemistry. A gradient in vegetation composition, water chemistry and dissolved organic matter characteristics followed a toposequence from the ombrotrophic bogs near the crest of the complex to poor fens at its downslope margins. We found that pore waters in poor fens contained elevated levels of MeHg, and the water draining from these features had dissolved MeHg concentrations 4.5 to 14.5 times higher than the water draining from the bogs. It was determined through analysis of historical aerial images that the poor fens in the toposequence had formed relatively recently (early 1970s) as a result of permafrost thaw. Differences between the fens and bogs are likely to be a result of their differences in groundwater function, and this suggests that permafrost thaw in this landscape can result in hotspots for Hg methylation that are hydrologically connected to downstream ecosystems. Copyright © 2016 John Wiley & Sons, Ltd.     

The role of baseflow in dissolved solids delivery to streams in the Upper Colorado River Basin

Salinity has a major effect on water users in the Colorado River Basin, estimated to cause almost $300 million per year in economic damages. The Colorado River Basin Salinity Control Program implements and manages projects to reduce salinity loads, investing millions of dollars per year in irrigation upgrades, canal projects, and other mitigation strategies. To inform and improve mitigation efforts, there is a need to better understand sources of salinity to streams and how salinity has changed over time. This study explores salinity in the baseflow fraction of streamflow, assessing whether groundwater is a significant contributor of dissolved solids to streams in the Upper Colorado River Basin (UCRB). Chemical hydrograph separation was used to estimate baseflow discharge and baseflow dissolved solids loads at stream gages (n = 69) across the UCRB. On average, it is estimated that 89% of dissolved solids loads originate from the baseflow fraction of streamflow, indicating that subsurface transport processes play a dominant role in delivering dissolved solids to streams in the UCRB. A statistical trend analysis using weighted regressions on time, discharge, and season was used to evaluate changes in baseflow dissolved solids loads in streams (n = 27) from 1986 to 2011. Decreasing trends in baseflow dissolved solids loads were observed at 63% of streams. At the three most downstream sites, Green River at Green River, UT, Colorado River at Cisco, UT, and the San Juan River near Bluff, UT, baseflow dissolved solids loads decreased by a combined 823,000 metric tons (mT), which is approximately 69% of projected basin‐scale decreases in total dissolved solids loads as a result of salinity control efforts. Decreasing trends in baseflow dissolved solids loads suggest that salinity mitigation projects, landscape changes, and/or climate are reducing dissolved solids transported to streams through the subsurface. Notably, the pace and extent of decreases in baseflow dissolved solids loads declined during the most recent decade; average decreasing loads during the 2000s (28,200 mT) were only 54% of average decreasing loads in the 1990s (51,700 mT).     

A long‐term study of stable isotopes as tracers of processes governing water flow and quality in a lowland river basin: the upper Thames,UK

A long‐term study of O, H and C stable isotopes has been undertaken on river waters across the 7000‐km² upper Thames lowland river basin in the southern UK. During the period, flow conditions ranged from drought to flood. A 10‐year monthly record (2003–2012) of the main River Thames showed a maximum variation of 3‰ (δ¹⁸O) and 20‰ (δ²H), although interannual average values varied little around a mean of –6.5‰ (δ¹⁸O) and –44‰ (δ²H). A δ²H/δ¹⁸O slope of 5.3 suggested a degree of evaporative enrichment, consistent with derivation from local rainfall with a weighted mean of –7.2‰ (δ¹⁸O) and –48‰ (δ²H) for the period. A tendency towards isotopic depletion of the river with increasing flow rate was noted, but at very high flows (>100 m³/s), a reversion to the mean was interpreted as the displacement of bank storage by rising groundwater levels (corroborated by measurements of specific electrical conductivity). A shorter quarterly study (October 2011–April 2013) of isotope variations in 15 tributaries with varying geology revealed different responses to evaporation, with a well‐correlated inverse relationship between Δ¹⁸O and baseflow index for most of the rivers. A comparison with aquifer waters in the basin showed that even at low flow, rivers rarely consist solely of isotopically unmodified groundwater. Long‐term monitoring (2003–2007) of carbon stable isotopes in dissolved inorganic carbon (DIC) in the Thames revealed a complex interplay between respiration, photosynthesis and evasion, but with a mean interannual δ¹³C‐DIC value of –14.8 ± 0.5‰, exchange with atmospheric carbon could be ruled out. Quarterly monitoring of the tributaries (October 2011–April 2013) indicated that in addition to the aforementioned factors, river flow variations and catchment characteristics were likely to affect δ¹³C‐DIC. Comparison with basin groundwaters of different alkalinity and δ¹³C‐DIC values showed that the origin of river baseflow is usually obscured. The findings show that long‐term monitoring of environmental tracers can help to improve the understanding of how lowland river catchments function. Copyright © NERC 2015. Hydrological Processes © 2015 John Wiley & Sons, Ltd.     

Modelling spatial variations in dissolved oxygen in fine‐grained streams under uncertainty

This paper presents a novel triple‐layer model, called VART DO‐3L, for simulation of spatial variations in dissolved oxygen (DO) in fine‐grained streams, characterized by a fluid mud (fluff or flocculent) layer (an advection‐dominated storage zone) as the interface between overlying stream water and relatively consolidated streambed sediment (a diffusion‐dominated storage zone). A global sensitivity analysis is conducted to investigate the sensitivity of VART DO‐3L model input parameters. Results of the sensitivity analysis indicate that the most sensitive parameter is the relative size of the advection‐dominated storage zones (A_s/A), followed by a lumped reaction term (R) for the flocculent layer, biological reaction rate (μ_o) in diffusive layer and biochemical oxygen demand concentration (L) in water column. In order to address uncertainty in model input parameters, Monte Carlo simulations are performed to sample parameter values and to produce various parameter combinations or cases. The VART DO‐3L model is applied to the Lower Amite River in Louisiana, USA, to simulate vertical and longitudinal variations in DO under the cases. In terms of longitudinal variation, the DO level decreases from 7.9 mg l at the Denham Springs station to about 2.89 mg l^?1 at the Port Vincent station. In terms of vertical variation, the DO level drops rapidly from the overlying water column to the advection‐dominated storage zone and further to the diffusive layer. The DO level (C_F) in the advective layer (flocculent layer) can reach as high as 40% of DO concentration (C) in the water column. The VART DO‐3L model may be applied to similar rivers for simulation of spatial variations in DO level. Copyright © 2014 John Wiley & Sons, Ltd.     

Dissolved organic matter in surface runoff in the Loess Plateau of China: The role of rainfall events and land-use

Exploring the chemical characterization of dissolved organic matter (DOM) is important for understanding the fate of laterally transported organic matter in watersheds. We hypothesized that differences in water-extractable organic matter (WEOM) in soils of varying land uses and rainfall events may significantly affect the quality and the quantity of stream DOM. To test our hypotheses, characteristics of rainfall-runoff DOM and WEOM of source materials (topsoil from different land uses and gullies, as well as typical vegetation) were investigated at two adjacent catchments in the Loess Plateau of China, using ultraviolet–visible absorbance and excitation emission matrix fluorescence with parallel factor analysis (PARAFAC). Results indicated that land-use types may significantly affect the chemical composition of soil WEOM, including its aromaticity, molecular weight, and degree of humification. The PARAFAC analysis demonstrated that the soils and stream water were dominated by terrestrial/allochthonous humic-like substances and microbial transformable humic-like fluorophores. Shifts in the fluorescence properties of stream DOM suggested a pronounced change in the relative proportion of allochthonous versus autochthonous material under different rainfall patterns and land uses. For example, high proportions of forestland could provide more allochthonous DOM input. This study highlights the relevance of soils and hydrological dynamics on the composition and fluxes of DOM issuing from watersheds. The composition of DOM in soils was influenced by land-use type. Precipitation patterns influenced the proportion of terrestrial versus microbial origins of DOM in surface runoff. Contributions of allochthonous, terrestrially derived DOM inputs were highest from forested landscapes.     

Suspended sediment and total dissolved solid yield patterns at the headwaters of Urumqi River,northwestern China: a comparison between glacial and non‐glacial catchments

In order to understand the differences in the suspended sediment and total dissolved solid (TDS) yield patterns between the glacial and non‐glacial catchments at the headwaters of Urumqi River, northwestern China, water samples were collected from a glacier catchment and an empty cirque catchment within the region, during three melting seasons from 2006 to 2008. These samples were analyzed to estimate suspended sediment and TDS concentrations, fluxes and erosion rates in the two adjoining catchments. There were remarked differences in suspended sediment and TDS yield patterns between the two catchments. Suspended sediment concentrations were controlled mainly by the sediment source, whereas TDS concentrations were primarily related to the hydrologic interaction with soil minerals. Generally, the glacial catchment had much higher suspended sediment and TDS yields, together with higher denudation rates, than the non‐glacial catchment. Overall, glacial catchment was mainly dominated by physical denudation process, whereas the non‐glacial catchment was jointly influenced by physical and chemical denudation processes. The observed differences in material delivery patterns were mainly controlled by the runoff source and the glacial processes. The melting periods of glacier and snow were typically the most important time for the suspended sediment and TDS yields. Meanwhile, episodic precipitation events could generate disproportionately large yields. Subglacial hydrology dynamics, glaciers pluck and grind processes could affect erodibility, and the large quantities of dust stored on the glacier surface provided additional sources for suspended sediment transport in the glacial catchment. These mechanisms imply that, in response to climate change, the catchment behaviour will be modified significantly in this region, in terms of material flux. Copyright © 2013 John Wiley & Sons, Ltd.     

Dissolved inorganic carbon evolution in neutral discharge from mine tailings piles

We measured the concentrations of dissolved inorganic carbon (DIC) and major ions and the stable carbon isotope ratios of DIC (δ¹³C_DIC) in two creeks discharging from carbonate‐rich sulphide‐containing mine tailings piles. Our aim was to assess downstream carbon evolution of the tailings discharge as it interacted with the atmosphere. The discharge had pH of 6.5–8.1 and was saturated with respect to carbonates. Over the reach of one creek, the DIC concentrations decreased by 1.1 mmol C/l and δ¹³C_DIC increased by ~4.0‰ 200 m from the seep source. The decrease in the DIC concentrations was concomitant with decreases in the partial pressure of CO_2(aq) because of the loss of excess CO_2(aq) from the discharge. The corresponding enrichment in the δ¹³C_DIC is because of kinetic isotope fractionation accompanying the loss of CO_2(g). Over the reach of the other creek, there was no significant decrease in the DIC concentrations or notable changes in the δ¹³C_DIC. The insignificant change in the DIC concentrations and the δ¹³C_DIC is because the first water sample was collected 160 m away from the discharge seep, not accessible during this research. In this case, most of the excess CO_2(aq) was lost before our first sampling station. Our results indicate that neutral discharges from tailings piles quickly lose excess CO_2(aq) to the atmosphere and the DIC becomes enrich in ¹³C. We suggest that a significant amount of carbon cycling in neutral discharges from tailings piles occur close to the locations where the discharge seeps to the surface. Copyright © 2015 John Wiley & Sons, Ltd.     

Changes in dissolved organic matter (DOM) amount and composition along nested headwater stream locations during baseflow and stormflow

Amount and composition of dissolved organic matter (DOM) were evaluated for multiple, nested stream locations in a forested watershed to investigate the role of hydrologic flow paths, wetlands and drainage scale. Sampling was performed over a 4‐year period (2008–2011) for five locations with drainage areas of 0.62, 3.5, 4.5, 12 and 79 ha. Hydrologic flow paths were characterized using an end‐member mixing model. DOM composition was determined using a suite of spectrofluorometric indices and a site‐specific parallel factor analysis model. Dissolved organic carbon (DOC), humic‐like DOM and fluorescence index were most sensitive to changes with drainage scale, whereas dissolved organic nitrogen, specific UV absorbance, Sr and protein‐like DOM were least sensitive. DOM concentrations and humic‐like DOM constituents were highest during both baseflow and stormflow for a 3.5‐ha catchment with a wetland near the catchment outlet. Whereas storm‐event concentrations of DOC and humic DOM constituents declined, the mass exports of DOC increased with increasing catchment scale. A pronounced dilution in storm‐event DOC concentration was observed at peak stream discharge for the 12‐ha drainage location, which was not as apparent at the 79‐ha scale, suggesting key differences in supply and transport of DOM. Our observations indicate that hydrologic flow paths, especially during storms, and the location and extent of wetlands in the catchment are key determinants of DOM concentration and composition. This study furthers our understanding of changes in DOM with drainage scale and the controls on DOM in headwater, forested catchments. Copyright © 2014 John Wiley & Sons, Ltd.