Sulfur and Oxygen Isotope Compositions of Dissolved Sulfate in the Yangtze River during High Water Period and Its Sulfate Source Tracing
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摘要: 碳酸盐岩的硫酸风化机制及其与碳循环的关系是全球碳循环研究中最为关注的科学问题之一, 其关键问题是识别硫酸盐来源.通过分析长江干流丰水期SO42-浓度及其硫、氧同位素组成特征, 探讨长江硫酸盐的来源及其主要控制因素.长江河水SO42-含量呈现逐年增加的趋势, 并且年增幅度逐渐加大.δ34SSO4和δ18OSO4变化范围为-3.5‰~5.6‰和3.7‰~9.2‰, 二者呈现显著的线性负相关关系.δ18OSO4值从上游到下游的增加趋势受长江水δ18OH2O值的空间组成特征的影响.研究表明, 大气降水(酸雨)和硫化物氧化是控制长江干流丰水期河水硫、氧同位素组成及其来源的主要机制, 为研究长江流域化学风化侵蚀作用和碳循环过程提供重要的理论依据.Abstract: Crustal weathering by sulfuric acid and its relationship with carbon cycling is a subject of greatest concern in the domain of global carbon cycling, with its key issue of the identification of riverine sulfate sources. In this study, stable sulfur and oxygen isotope compositions of riverine sulfate in the mainstream of the Yangtze River during rainy season are determined to trace the riverine sulfate sources and controlling factors. The SO42-concentration keeps increasing with ever-increasing annual growth rate. The isotope compositions of dissolved sulfate in the Yangze River range from -3.5‰ to 5.6‰ for δ34SSO4 and from 3.7‰ to 9.2‰ for δ18OSO4, showing a significantly negative linear correlation between δ34SSO4 and δ18OSO4. The tendency of increased δ18OSO4 values from upstream to downstream is controlled by δ18OH2O values of the Yangtze River water. It is indicated that atmospheric acid deposition and sulfide oxidation are dominant sources of dissolved sulfate in the Yangze River. This study offers theoretical basis which facilitates further environmental explorations for chemical weathering of carbonate and carbon cycling.
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Key words:
- sulfur isotope /
- oxygen isotope /
- sulfate source /
- the Yangtze River /
- geochemistry
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图 1 长江流域采样点分布(据丁悌平等(2013)修改)
Fig. 1. A sketch map of the Yangtze River drainage area with sampling locations
图 2 长江干流丰水期河水SO42-浓度沿径流途径的变化曲线
Fig. 2. Plots showing spatial variations of SO42- concentrations from the mainstream of the Yangtze River during high water period
图 3 长江干流丰水期河水硫酸盐硫和氧同位素组成沿径流途径的变化曲线
Fig. 3. The special δ34SSO4 and δ18OSO4 variations of dissolved sulfate in the water from the mainstream of the Yangtze River during high water period
图 4 长江干流丰水期SO42-的δ34SSO4和δ18OSO4关系
Fig. 4. δ34SSO4 vs. δ18OSO4 of dissolved sulfate in the water of the Yangtze River during high water period
图 5 长江水的δ18OH2O与硫酸盐的δ18OSO4的关系
Fig. 5. δ18OH2O of water vs. δ18OSO4 of dissolved sulfate in the water of the Yangtze River
表 1 长江干流丰水期河水主要离子与同位素组成的分析结果
Table 1. Chemical and isotopic compositions of Yangtze River during high water period
样品编号 采集时间 采样地点 经纬度坐标 pH EC(μS/cm) SO42- Cl- HCO3- K++Na+ Ca2+ Mg2+ δ34SSO4(‰ vs. VCDT) δ18OSO4(‰ vs. VSMOW) δ18OH2O(‰ vs. VSMOW) (mg/L) CJ1 2013.8.14 宜宾 E104°36′50.65″, N28°45′23.84″ 8.19 317 37.3 24.9 124.4 22.4 31.3 7.7 3.5 5.0 -14.6 CJ2 2013.8.15 泸州 E105°26′07.41″, N28°52′13.31″ 8.07 306 37.9 20.1 127.7 19.8 32.1 7.5 -0.8 5.9 -13.9 CJ3 2013.8.16 重庆 E106°31′28.72″, N29°31′39.03″ 7.90 319 41.3 19.4 129.6 19.4 34.6 7.3 2.7 5.0 -13.7 CJ4 2013.8.17 涪陵 E107°23′20.32″, N29°42′53.31″ 7.96 312 39.5 18.0 128.3 18.0 35.4 7.3 - - -13.2 CJ5 2013.8.19 万州 E108°22′54.51″, N30°48′34.17″ 7.88 312 28.8 14.6 127.0 17.0 36.0 6.9 0.8 6.0 -12.7 CJ6 2013.8.20 奉节 E109°27′23.70″, N31°00′05.66″ 7.86 319 41.9 16.8 132.9 17.0 36.8 6.8 1.5 6.9 -12.7 CJ7 2013.8.20 巴东 E110°19′46.73″, N31°02′55.35″ 7.80 328 45.4 15.0 130.3 16.0 39.6 6.8 5.4 4.5 -11.9 CJ8 2013.8.20 宜昌 E111°16′50.94″, N30°45′16.03″ 8.01 329 43.1 16.4 133.6 17.6 37.6 7.2 3.7 5.7 -11.8 CJ9 2013.8.22 沙市 E112°14′19.51″, N30°18′22.67″ 7.84 335 42.2 17.3 128.3 17.0 37.0 7.0 5.2 3.7 -11.1 CJ23 2013.8.14 监利 E110°03′51.87″, N29°26′44.78″ 7.96 324 36.1 14.8 130.0 17.4 37.3 6.9 -0.4 8.0 -11.5 CJ10 2013.8.23 岳阳 E113°31′00.27″, N29°49′53.60″ 7.88 312 30.4 14.2 124.1 16.5 36.4 6.6 1.3 7.6 -12.3 CJ11 2013.8.22 洪湖 E114°14′27.08″, N30°30′15.16″ 7.88 321 30.7 15.3 130.6 15.1 31.3 5.6 -3.5 9.2 -10.1 CJ12 2013.8.22 武汉 E115°03′58.39″, N30°14′48.88″ 7.82 312 33.3 12.6 126.7 14.5 38.9 6.3 5.6 5.2 -10.7 CJ13 2013.8.7 黄石 E116°00′32.40″, N29°44′30.52″ 7.77 313 35.8 12.4 128.3 15.1 38.3 6.4 3.8 7.0 -10.3 CJ14 2013.8.6 九江 E117°03′09.14″, N30°30′10.59″ 7.73 293 34.5 11.8 117.3 14.2 35.5 6.0 -0.5 8.0 -9.5 CJ15 2013.8.5 安庆 E117°43′51.69″, N30°51′09.96″ 7.78 304 33.9 12.7 123.8 14.7 36.5 6.0 4.8 5.1 -9.6 CJ16 2013.8.4 铜陵 E118°21′03.37″, N31°20′21.64″ 7.73 306 35.0 12.9 122.2 15.1 37.7 6.1 -0.3 7.0 -9.5 CJ17 2013.8.4 芜湖 E118°29′11.98″, N31°45′58.97″ 7.73 317 36.8 13.0 126.7 14.9 39.0 6.4 -1.5 8.4 -9.4 CJ18 2013.8.3 马鞍山 E118°37′08.29″, N31°56′32.31″ 7.73 319 38.0 12.8 128.7 14.8 39.7 6.5 2.4 6.3 -8.5 CJ19 2013.8.2 南京 E119°22′47.55″, N32°13′55.79″ 7.73 330 39.3 15.1 123.1 17.4 39.1 6.6 0.8 6.3 -9.1 CJ20 2013.7.31 镇江 E120°48′09.53″，N32°01′03.04″ 7.81 319 36.9 15.4 114.0 21.3 45.7 7.6 -0.8 8.4 -9.2 CJ21 2013.7.30 南通 E121°36′44.00″, N31°21′29.00″ 7.58 409 37.4 34.9 123.5 35.4 39.4 7.4 1.7 7.0 -8.4 CJ22 2013.7.28 上海 E113°01′25.00″, N29°31′44.50″ 7.78 338 48.9 13.5 137.5 17.0 39.7 7.0 -2.3 8.8 -7.6 
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表 2 铜陵-芜湖段SO42-含量与历史数据的对比
Table 2. Comparisons of SO42- concentration and its growth rate in the lower Tongling-Wuhu area
取样地点 取样时间 SO42-(mg/L) 年增幅(mg/(L·a)) 铜陵-芜湖段 2013年8月 35.0~36.8(35.9)a 1.00b 大通附近 2007年7月 29.6~30.1(29.9)(夏学齐等, 2008) 0.85c 大通 1958—1990年平均值 11.9(Chen et al., 2002) 0.22d a.本研究的数据，括号内为铜陵-芜湖段数据的平均值；b.2007—2013年的SO42-增加速率；c.1990—2007年的SO42-增加速率.其中，1990年SO42-含量(15.4mg/L)是结合1958—1990年SO42-含量平均值(11.9mg/L)及其年增幅估算的；d.1958—1990年的SO42-增加速率，数据来源于 Chen et al.(2002) .
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