Spatiotemporal variations of nitrate sources and dynamics in a typical agricultural riverine system under monsoon climate

Nitrogen pollution is a serious environmental issue in the Danjiangkou Reservoir region (DRR), the water source of the South-to-North Water Diversion Project of China. In this research, seasonal surveys and a bi-weekly time series survey were conducted in the Qihe River Basin, one of the most densely populated agricultural basins in the DRR. Hydrochemical compositions (NO₃^? and Cl^?), dual isotopes (δD-H₂O, δ¹⁸O-H₂O, δ¹⁵N-NO₃^?, and δ¹⁸O-NO₃^?), and a Markov Chain Monte Carlo isotope mixing model were jointly applied to unravel the sources, migrations, and transformations of the nitrate (NO₃^?) in the basin. It was revealed that the mixing between different sources was the main process controlling the isotopic compositions of the riverine NO₃^? in the upper-middle reaches. In contrast, denitrification occurred in the lower reaches. For the first time, the sources of NO₃^? were quantified at a basin scale in the DRR. Overall, the river transported 484.2 tons/year of NO₃-N to the reservoir, of which 32.6%, 36.4%, 28.0%, and 3.0% was from soil organic nitrogen, chemical fertilizer, residential sewage and atmospheric precipitation, respectively. The NO₃-N fluxes of the different sources were regulated by the monsoon climate and anthropogenic activities. For example, high precipitation and intense fertilization resulted in severe nonpoint source pollution. Denitrification thrived in soils and reservoirs in wet seasons. Temperature could regulate the migration, nitrification and denitrification processes. Based on the results, we suggest that the management strategies dealing with nitrogen pollution issue in the DRR should follow the specific spatiotemporal characteristics of NO₃^? sources, migration and transformation mechanisms.     

锆负载颗粒沸石改良底泥对水中磷酸盐的吸附行为

通过批量吸附实验考察了锆负载颗粒沸石改良底泥对水中磷酸盐的吸附特征,并采用分级提取法分析了被改良底泥中锆负载颗粒沸石所吸附磷酸盐的形态分布特征.结果发现,与Freundlich和Dubinin-Radushkevich模型相比,Langmuir模型可以更好地用于描述改良底泥对水中磷酸盐的吸附等温行为.改良底泥对水中磷酸盐的吸附动力学过程可以较好地采用准二级动力学模型和Elovich模型加以描述,膜扩散和颗粒内扩散共同构成了缓慢吸附阶段速率的限制步骤.溶液共存的SO_4~(2-)和HCO_3~-降低了改良底泥对水中磷酸盐的吸附,而共存的Na~+、K~+、Mg~(2+)和Ca~(2+)却增强了对磷酸盐的吸附,且Ca~(2+)的增强效果大于Mg~(2+),后者的增强效果又大于Na~+和K~+.改良底泥对水中磷酸盐的吸附能力明显强于未改良底泥,前者的最大单位吸附量为336 mg·kg~(-1),明显高于后者的最大单位吸附量(215 mg·kg~(-1)).被改良底泥中锆负载颗粒沸石所吸附的磷酸盐主要以较为稳定的NaOH-P和最为稳定的Res-P形态存在,不容易被重新释放出来.上述的研究结果显示,向底泥中添加锆负载颗粒沸石可以显著增加底泥对水中磷酸盐的吸附能力,锆负载颗粒沸石是一种有希望的可以用于底泥内源磷释放控制的底泥改良剂.     

外加锌在土壤中形态的研究

本文采用化学逐级提取法对吸附锌后的土壤分别提取了交换态、CaCO_3结合态、氧化物结合态和有机质结合态的锌量,并讨论pH、温度和溶液中锌离子浓度对不同形态锌分布的影响。实验结果表明:外加锌被石灰性土壤吸附后,高pH值(7.5)时形态分布为:CaCO_3结合态≥交换态>氧化物结合态>有机质结合态;低pH值(5.5)时则为:交换态>CaCO_3结合态>氧化物结合态>有机质结合态。各形态锌的分配系数还受到吸附时的温度和溶液中锌离子浓度的影响。     

大气CO2浓度升高对农田土壤颗粒组成及其碳周转的影响

采集FACE(Free Air CO2 Enrichment)平台下运行3年的水稻(Oryza sativaL.)/小麦(Triticum aestivumL.)轮作土壤(0~15cm耕作层土壤),利用超声波分散-湿筛分法对烘干土样进行颗粒分级,分析土壤各粒级及其碳、氮的分布特征,研究大气CO2浓度升高对土壤碳周转的影响。结果表明:高浓度大气CO2条件下稻/麦轮作3年后,土壤颗粒组成较对照发生了改变,>53μm粒级的质量分数减小27%(p<0.05),约占土壤总质量20%;53~25μm粒级的质量分数增大35%(p<0.05),约占土壤总质量25%;<25μm无明显变化,约占土壤总质量55%,三种粒级之间质量分数呈显著差异(p<0.05)。FACE条件下,不同粒级土壤颗粒碳质量分数在两个氮水平下平均为:>53μm(30.60g·kg-1),<25μm(13.08g·kg-1),25~53μm(12.85g·kg-1),氮质量分数分别为2.42g·kg-1,1.33g·kg-1,1.12g·kg-1。>53μm粒级的土壤颗粒碳、氮质量分数均极显著高于其它两个粒级(p<0.001)。FACE条件下土壤总碳、氮质量分数高于对照,增幅分别为6.2%和6.7%。从各粒级土壤颗粒碳、氮质量分数变化分析,新增碳、氮主要进入>53μm粒级中,表明该粒级土壤颗粒对土壤碳氮循环(转化和保存)起着重要作用。该研究结果表明高浓度大气CO2条件下,稻/麦轮作农田土壤将成为大气CO2的汇,这将为预测我国未来农田土壤碳的变化趋势提供科学依据。     

Characterization of environmental water samples using strontium and lead stable isotope compositions

A simple procedure using both cation and anion exchange chromatography has been applied in the study of lead and strontium isotope composition in rain and stream water samples from remote catchments in Scotland. Whereas the soil released strontium to stream waters, lead was removed from rain water and the concentrations in stream waters were very low. Highly precise analysis by thermal ionisation mass spectrometry proved necessary in the determination of strontium isotope composition. The ⁸⁷Sr/⁸⁶Sr ratio in rain water was close to that of marine strontium but the ratios in stream waters were constant and highly characteristic for the stream. In the case of the stream at the Sourhope site, the ratio (0.70798 ± 0.00005) was less than that in rain water and probably resulted from the weathering of one specific mineral. The results suggested that the ⁸⁷Sr/⁸⁶Sr ratios could be used as a stable isotope tracer of waters and to provide information on the weathering processes. Two major anthropogenic components of lead were identified in water samples. One had its origin in petrol additives whereas the other was probably of industrial origin. The low ²⁰⁶Pb/²⁰⁷Pb ratios observed in stream waters confirmed the lead as being of anthropogenic origin and the data suggested that there was a movement, albeit very small, of lead from the soil to waters.     

Copper, Lead and Zinc Mobility and Bioavailability in a River Sediment Contaminated with Paint Stripping Residue

A river embankment sediment beneath a road bridge in South Australia had been surveyed on a previous occasion to a depth of 10 cm and found to contain high levels of copper, lead and zinc deposited during previous lead and zinc-based primer paint stripping operations prior to repainting the bridge. Since the river embankment is geologically different from the surrounding non-embankment soils, and a sufficient distance from the bridge along the river embankment could not be traversed, the geological background Cu, Pb and Zn fraction was established initially using a solid phase sequential extraction (SPSE) procedure. Assessment of the degree of contamination and extent of vertical mobility was then established. Copper was a minor contaminant and present predominantly as the geological background species. Lead was partitioned evenly between the oxalate soluble fraction and residual fraction to a depth of 30 cm with a decrease in total Pb concentration from 497 to 141 mg Pb kg^–1 while Zn was predominantly in the oxalate soluble fraction to a depth of 15cm with a decrease in concentration from 1013 to 150 mg Zn kg^–1. The reduced rate of nitrification and the lower total concentration of NO₃ ^–-N together with the higher respiratory quotient, combined with the lower microbial quotient, are indicative of microbial stress due to heavy metal toxicity. In the case of Pb and Zn paint stripping residues, these changes in indicators of microbial health are possibly the result of the greater abundance and hence possible bioavailabilty of organo- and chloro-Pb compared to organo- and chloro-Zn complexes.     

地幔流体的稳定同位素地球化学综述

总结了 2 0年来国内外学者对地幔流体研究的成果和认识。主要包括地幔流体的性质和组成 ;地幔流体中同位素的含量、组成和赋存形式 ;同位素分馏和地幔脱气等作用对地幔组分的影响等。在不同地区和不同构造环境条件的地幔流体中 ,各种组分含量和同位素组成变化可以很大 ,从一个侧面指示地幔组分的不均一性 ,反映了不同地幔物质的形成历程不同或来自不同的地幔源区。此外 ,还讨论了目前存在的几个疑点     

Atmospheric Dust Loads and Their Elemental Composition at a Background Site in India

Air particulate samples collected during 1995–96 ata background site situated on the east coast of Thar Desert inRajsthan State of India were analysed for atmospheric dustloads (Suspended Particulate Matter) and elemental composition.The values of SPM ranged from 9 g M^-3 to 97g M^-3 with an average of 43 g M^-3 except a fewepisodic values, which were 3 to 5 times higher than the averageduring summer months. The results for elemental composition ofthe particulate samples showed that the concentrations ofanthropogenic toxic trace elements viz. Br, Cr, Pb, Sb, Se and Znare lower by a factor of 2 to 10 as compared to urban areas. Thehigh enrichment factors for anthropogenic elements viz. Br, Pb,Sb and Zn show an input from coal/wood fuel burning andvehicular pollution at the sampling site. The depletion of Si inSPM samples shows long distance transport of dust to the samplingsite.     

Sequential fractionation of phosphorus in lake sediments of Northern Greece

The amounts and forms of potentially mobile P in surface sediments from two lakes, Volvi and Koronia, located in Northern Greece were evaluated using a sequential chemical extraction. Five sedimentary P reservoirs were separately quantified: loosely sorbed P (NH₄Cl-P); iron associated P (BD-P); calcium bound P (HCl-P); metal oxide bound P (NaOH-P) and residual P (organic and refractory P). Samples were taken in two seasons and the average concentration of the fractions of phosphorus were calculated. The results indicated that the TP content and chemically extractable phosphorus in the sediments of Koronia Lake were higher than those of Volvi Lake. Sediment TP was also strongly and positively correlated with sediment Fe. Fine-sized sediments exhibited significantly higher concentrations for both lakes than the sand fraction. The P in the surface sediment mainly consisted of HCl-P and Res-P, while NH₄Cl-P and BD-P only constituted a minor part. The rank order of the different P extracts was the same for the two lakes and was Residual-P > HCl-P > NaOH-P > BD-P > NH₄Cl-P.     

Estrogenic and dioxin-like compounds in sediment from Zierikzee harbour identified with CALUX assay-directed fractionation combined with one and two dimensional gas chromatography analyses

The identity of compounds responsible for estrogenic and dioxin-like activities in sediment from the harbour of the small town Zierikzee in Zeeland, The Netherlands, was investigated using a bioassay directed fractionation approach with the in vitro estrogen and dioxin responsive reporter gene assays ER- and DR-CALUX. For identification of compounds exhibiting activity in the bioassays, either one or two-dimensional GC in combination with quadrupole (MSD), ion trap (ITD) or time-of-flight mass spectrometric detection (ToF-MS) was used, depending on the biological and chemical characteristics and the complexity of the fractions. The natural estrogenic hormone 17-β-estradiol and its metabolite estrone were identified with GC–ITD as the main contributors to the estrogenic activity. After successive rounds of fractionation, the dioxin-like activity could be explained by the presence of various polycyclic aromatic hydrocarbons identified with GC–MSD and two-dimensional comprehensive GC × GC–ToF-MS. Some estrogenic activity of a relatively non-polar nature remained unidentified.