海水中过氧化氢的研究进展

doi:10.11867/j.issn.1001-8166.2014.07.0765

海水中过氧化氢（H₂O₂）能与多种痕量金属发生氧化还原反应并改变其存在状态,从而间接影响海洋生态系统。综述了过去30多年的研究结果并提出进一步研究方向。H₂O₂在100~200 m以浅的上层海洋中普遍存在,浓度介于0~10² nmol/L之间。H₂O₂在表层含量最高,随深度增加而减小;近岸海区H₂O₂浓度通常高于寡营养大洋;并且海水中H₂O₂出现典型的周日波动（白天浓度增加,于午后达到最大值后逐渐降低,至黎明达到最低值）。海水中H₂O₂的来源包括光化学生产、大气沉降和生物生产,一般以光化学生产为主。去除过程包括生物分解、光化学分解和化学分解,以生物分解为主。目前对H₂O₂在受河流影响的近岸陆架海区中的生物地球化学、光化学生产的影响因素以及H₂O₂的去除机制尚缺乏全面认识,在这些方面还需更多研究。

关键词: 光化学, 溶解有机物, 周日变化, 降雨, 浮游生物

Hydrogen peroxide can oxidize or reduce a number of biological important trance metals in seawater. Therefore, it can indirectly affect the marine ecosystem by causing the changes in the speciation of these metals. The results of researches about hydrogen peroxide in seawater in the last more than thirty years were reviewed and the direction of study in the further was proposed in this paper. Hydrogen peroxide can be found rather ubiquitously in the upper water at concentration of 0~102 nmol/L. In water column the maximum of the concentrations of hydrogen peroxide presents in surface water and the concentrations decrease with the increase of depth. In general, the concentrations in costal seawater are higher than these in the oligotrophic ocean. Diel variation of hydrogen peroxide occurs in seawater: the concentrations increase since sunup until the mixmum of afternoon and decrease until the minimum at drawn. The sources of hydrogen peroxide in marine environment include photochemical production, atmospheric deposition and biological production, and the photochemical production is primary among them. The sinks of hydrogen peroxide in the ocean consist of biological and chemical and photochemical decomposition and the main one is biological decomposition. The biogeochemistry of hydrogen peroxide in the continental shelf influenced by river water and factors affecting photochemical production and detail of decomposition should be studied in the future.

Key words: Photochemistry, Dissolved organic matter, Diel variation, Rain, Phytoplankton.

中图分类号:

P734

表1 不同海区表层水H ₂O ₂浓度

Table 1 The concentration of H ₂O ₂ in surface seawater

海区	浓度（nmol/L)	参考文献
大洋
大西洋南部和中部	20~80	^{[ 34 ]}
西北太平洋<br/>BATS	10~250<br/>8月:80~200; 3月: 40~70	^{[ 37 ]}<br/>^{[ 28 ]}
赤道大西洋	31~150	^{[ 35 ]}
大西洋东部	21~123	^{[ 38 ]}
大西洋	30~160	^{[ 50 ]}
赤道太平洋	40~70	^{[ 51 ]}
南大洋印度扇形区	5~19.7	^{[ 52 ]}
马尾藻海	100~180	^{[ 46 ]}
近岸海区		<br/>
墨西哥湾<br/>地中海西部	100~280<br/>100~130	^{[ 22 ]}<br/>^{[ 48 ]}
加勒比海东部	春: 60~120; 秋: 95~420	^{[ 23 ]}
秘鲁上升流<br/>大堡礁<br/>南海北部	8~50<br/>15~110<br/>63~225	^{[ 47 ]}<br/>^{[ 49 ]}<br/>作者
河口
Port Hacking河口	12~116	^{[ 53 ]}
Patuxent River河口	11~350	^{[ 54 ]}
亚马逊河口	240	^{[ 35 ]}
亚马逊河口	约200	^{[ 34 ]}

表1 不同海区表层水H ₂O ₂浓度

Table 1 The concentration of H ₂O ₂ in surface seawater

海区	浓度（nmol/L)	参考文献
大洋
大西洋南部和中部	20~80	^{[ 34 ]}
西北太平洋<br/>BATS	10~250<br/>8月:80~200; 3月: 40~70	^{[ 37 ]}<br/>^{[ 28 ]}
赤道大西洋	31~150	^{[ 35 ]}
大西洋东部	21~123	^{[ 38 ]}
大西洋	30~160	^{[ 50 ]}
赤道太平洋	40~70	^{[ 51 ]}
南大洋印度扇形区	5~19.7	^{[ 52 ]}
马尾藻海	100~180	^{[ 46 ]}
近岸海区		<br/>
墨西哥湾<br/>地中海西部	100~280<br/>100~130	^{[ 22 ]}<br/>^{[ 48 ]}
加勒比海东部	春: 60~120; 秋: 95~420	^{[ 23 ]}
秘鲁上升流<br/>大堡礁<br/>南海北部	8~50<br/>15~110<br/>63~225	^{[ 47 ]}<br/>^{[ 49 ]}<br/>作者
河口
Port Hacking河口	12~116	^{[ 53 ]}
Patuxent River河口	11~350	^{[ 54 ]}
亚马逊河口	240	^{[ 35 ]}
亚马逊河口	约200	^{[ 34 ]}

图1 赤道大西洋H ₂O ₂和阳光短波辐射日变化 ^{[

34
]} ●：H₂O₂,—：短波太阳辐照强度(右侧坐标轴)

Fig. 1 Diurnal variations of the concentration of H ₂O ₂ and solar irradiance ●：H₂O₂,—：short wave solar radiation (right axis)

[1]	Petasne R G, Zika R G. Hydrogen peroxide lifetimes in south Florida coastal and offshore waters[J]. Marine Chemistry, 1997, 56(3/4): 215-225.
[2]	Yocis B H, Kieber D J, Mopper K. Photochemical production of hydrogen peroxide in Antarctic waters[J]. Deep Sea Research Part I: Oceanographic Research Papers, 2000, 47(6): 1077-1099.
[3]	Zhang L S, Wong G T F. Optimal conditions and sample storage for the determination of H2O2 in marine waters by the scopoletin-horseradish peroxidase fluorometric method[J]. Talanta, 1999, 48(5): 1031-1038.
[4]	González-Davila M, Santana-Casiano J M, Millero F J. Oxidation of iron (II) nanomolar with H2O2 in seawater[J]. Geochimica et Cosmochimica Acta, 2005, 69(1): 83-93.
[5]	Millero F J, Sotolongo S. The oxidation of Fe (II) with H2O2 in seawater[J]. Geochimica et Cosmochimica Acta, 1989, 53(8): 1867-1873.
[6]	Moffett J W, Zika R G. Reaction kinetics of hydrogen peroxide with copper and iron in seawater[J]. Environmental Science & Technology, 1987, 21(8): 804-810.
[7]	Santana-Casiano J M, Gonzalez-Davila M, Millero F J. The role of Fe (II) species on the oxidation of Fe (II) in natural waters in the presence of O2 and H2O2[J]. Marine Chemistry, 2006, 99(1/4): 70-82.
[8]	Du Zhiheng, Xiao Cunde, Li Xiangying. A review of the sources and controlling factors of bioavailibility iron (Fe)[J]. Advances in Earth Science, 2013,28(5):597-607.
	[杜志恒,效存德,李向应. 生物活性元素Fe来源及其溶解度影响因素研究综述[J]. 地球科学进展, 2013, 28(5): 597-607.]
[9]	Millero F J, Sharma V K, Karn B. The rate of reduction of copper (II) with hydrogen peroxide in seawater[J]. Marine Chemistry, 1991, 36(1/4): 71-83.
[10]	Sharma V K, Millero F J. The oxidation of Cu (I) with H2O2 in natural waters[J]. Geochimica et Cosmochimica Acta, 1989, 53(9): 2269-2276.
[11]	Pettine M, Millero F J. Chromium speciation in seawater: The probable role of hydrogen peroxide[J]. Limnology and Oceanography, 1990, 35(3): 730-736.
[12]	Pettine M, Millero F J, La Noce T. Chromium (III) interactions in seawater through its oxidation kinetics[J]. Marine Chemistry, 1991, 34(1/2): 29-46.
[13]	Pettine M, Millero F J. Effect of metals on the oxidation of As (III) with H2O2[J]. Marine Chemistry, 2000, 70(1/3): 223-234.
[14]	Sunda W G, Huntsman S A. Photoreduction of manganese oxides in seawater[J]. Marine Chemistry, 1994, 46(1/2): 133-152.
[15]	Pan Anyang, Yang Qunhui, Zhou Huaiyang, et al. Development of in-situ analyzing technologies of dissolved mangenes and iron in deep-sea seawater[J]. Advances in Earth Science, 2013, 28(4): 420-428.
	[潘安阳,杨群慧,周怀阳,等. 深海溶解态锰和铁的原位分析技术研究进展[J]. 地球科学进展, 2013, 28(4): 420-428.]
[16]	Wong G T F, Dunstan W M, Kim D B. The decomposition of hydrogen peroxide by marine phytoplankton: La décomposition du peroxyde d’hydrog ne par le phytoplancton marin[J]. Oceanologica Acta, 2003, 26(2): 191-198.
[17]	Willey J D, Kieber R J, Brooks Avery G. Effects of rainwater iron and hydrogen peroxide on iron speciation and phytoplankton growth in seawater near Bermuda[J]. Journal of Atmospheric Chemistry, 2004, 47(3): 209-222.
[18]	Lesser M. Oxidative stress causes coral bleaching during exposure to elevated temperatures[J]. Coral Reefs, 1997, 16(3): 187-192.
[19]	Higuchi T, Fujimura H, Arakaki T, et al. The synergistic effects of hydrogen peroxide and elevated seawater temperature on the metabolic activity of the coral Galaxea fascicularis[J]. Marine Biology, 2009, 156(4): 589-596.
[20]	Van Baalen C, Marler J E. Occurrence of hydrogen peroxide in sea water[J]. Nature, 1966, 211:951.
[21]	Miller G W, Morgan C A, Kieber D J, et al. Hydrogen peroxide method intercomparision study in seawater[J]. Marine Chemistry, 2005, 97(1/2): 4-13.
[22]	Zika R G, Moffett J W, Petasne R G, et al. Spatial and temporal variations of hydrogen peroxide in Gulf of Mexico waters[J]. Geochimica et Cosmochimica Acta, 1985, 49(5): 1173-1184.
[23]	Moore C A, Farmer C T, Zika R G. Influence of the Orinoco River on hydrogen peroxide distribution and production in the eastern Caribbean[J]. Journal of Geophysical Research, 1993, 98(C2): 2289-2298.
[24]	Cooper W J, Saltzman E S, Zika R G. The contribution of rainwater to variability in surface ocean hydrogen peroxide[J]. Journal of Geophysical Research, 1987, 92(C3): 2970-2980.
[25]	Scully N M, Vincent W F, Lean D R S, et al. Hydrogen peroxide as a natural tracer of mixing in surface layers[J]. Aquatic Sciences-Research Across Boundaries, 1998, 60(2): 169-186.
[26]	Kieber R J, Cooper W J, Willey J D, et al. Hydrogen peroxide at the Bermuda Atlantic Time Series Station. Part 1: Temporal variability of atmospheric hydrogen peroxide and its influence on seawater concentrations[J]. Journal of Atmospheric Chemistry, 2001, 39(1): 1-13.
[27]	Peake B M, Mosley L M. Hydrogen peroxide concentrations in relation to optical properties in a fiord (Doubtful Sound, New Zealand)[J]. New Zealand Journal of Marine and Freshwater Research, 2004, 38(4): 729-741.
[28]	Avery J G B, Cooper W J, Kieber R J, et al. Hydrogen peroxide at the Bermuda Atlantic Time Series Station: Temporal variability of seawater hydrogen peroxide[J]. Marine Chemistry, 2005, 97(3/4): 236-244.
[29]	Clark C D, De Bruyn W J, Jones J G. Photochemical production of hydrogen peroxide in size-fractionated Southern California coastal waters[J]. Chemosphere, 2009, 76(1): 141-146.
[30]	Andreae W A. A sensitive method for the estimation of hydrogen peroxide in biological materials[J]. Nature, 1955, 175:859.
[31]	Kieber R J, Helz G R. Two-method verification of hydrogen peroxide determinations in natural waters[J]. Analytical Chemistry, 1986, 58(11): 2312-2315.
[32]	Holm T R, George G K, Barcelona M J. Fluorometric determination of hydrogen peroxide in groundwater[J]. Analytical Chemistry, 1987, 59(4): 582-586.
[33]	Palenik B, Morel F M M. Dark production of H2O2 in the Sargasso Sea[J]. Limnology and Oceanography, 1988, 33(6): 1606-1611.
[34]	Yuan J, Shiller A M. The distribution of hydrogen peroxide in the southern and central Atlantic Ocean[J]. Deep Sea Research Part II: Topical Studies in Oceanography, 2001, 48(13): 2947-2970.
[35]	Croot P L, Streu P, Peeken I, et al. Influence of the ITCZ on H2O2 in near surface waters in the equatorial Atlantic Ocean[J]. Geophysical Research Letters, 2004, 31(23): L23S04, doi:10.1029/2004GL020154.
[36]	Yuan J, Shiller A M. Hydrogen peroxide in deep waters of the North Pacific Ocean[J]. Geophysical Research Letters, 2004, 31(1): L01310,doi:10.1029/2003GL018439.
[37]	Yuan J, Shiller A M. Distribution of hydrogen peroxide in the northwest Pacific Ocean[J]. Geochemistry Geophysics Geosystems, 2005, 6(9): Q09M02,doi:10.1029/2004GC000908.
[38]	Steigenberger S, Croot P. Identifying the processes controlling the distribution of H2O2 in surface waters along a meridional transect in the eastern Atlantic[J]. Geophysical Research Letters, 2008, 35(3): L03616,doi:10.1029/2007GL032555.
[39]	Price D, Mantoura R F C, Worsfold P J. Shipboard determination of hydrogen peroxide in the western Mediterranean sea using flow injection with chemiluminescence detection[J]. Analytica Chimica Acta, 1998, 371(2/3): 205-215.
[40]	Greenway G M, Leelasattarathkul T, Liawruangrath S, et al. Ultrasound-enhanced flow injection chemiluminescence for determination of hydrogen peroxide[J]. Analyst, 2006, 131(4): 501-508.
[41]	Yuan J, Shiller A M. Determination of subnanomolar levels of hydrogen peroxide in seawater by reagent-injection chemiluminescence detection[J]. Analytical Chemistry, 1999, 71(10): 1975-1980.
[42]	Cooper W J, Moegling J K, Kieber R J, et al. A chemiluminescence method for the analysis of H2O2 in natural waters[J]. Marine Chemistry, 2000, 70(1/3): 191-200.
[43]	Johnson K S, Sakamoto-Arnold C M, Willason S W, et al. Reagent-injection flow analysis: Application to the determination of nanomolar levels of hydrogen peroxide in seawater[J]. Analytica Chimica Acta, 1987, 201:83-94.
[44]	Bader H, Sturzenegger V, Hoigne J. Photometric method for the determination of low concentrations of hydrogen peroxide by the peroxidase catalyzed oxidation of N, N-diethyl-p-phenylenediamine (DPD)[J]. Water Research, 1988, 22(9): 1109-1115.
[45]	Olasehinde E F, Makino S, Kondo H, et al. Application of Fenton reaction for nanomolar determination of hydrogen peroxide in seawater[J]. Analytica Chimica Acta, 2008, 627(2): 270-276.
[46]	Miller W L, Kester D R. Peroxide variations in the Sargasso Sea[J]. Marine Chemistry, 1994, 48(1): 17-29.
[47]	Zika R G, Saltzman E S, Cooper W J. Hydrogen peroxide concentrations in the Peru upwelling area[J]. Marine Chemistry, 1985, 17(3): 265-275.
[48]	Johnson K S, Willason S W, Wiesenburg D A, et al. Hydrogen peroxide in the western Mediterranean Sea: A tracer for vertical advection[J]. Deep Sea Research Part I: Oceanographic Research Papers, 1989, 36(2): 241-254.
[49]	Szymczak R, Waite T D. Photochemical activity in waters of the Great Barrier Reef[J]. Estuarine, Coastal and Shelf Science, 1991, 33(6): 605-622.
[50]	Weller R, Schrems O. H2O2 in the marine troposphere and seawater of the Atlantic Ocean (48°N-63°S)[J]. Geophysical Research Letters, 1993, 20(2): 125-128.
[51]	Hanson A K, Tindale N W, Abdel-Moati M A R. An Equatorial Pacific rain event: Influence on the distribution of iron and hydrogen peroxide in surface waters[J]. Marine Chemistry, 2001, 75(1/2): 69-88.
[52]	Sarthou G, Jeandel C, Brisset L, et al. Fe and H2O2 distributions in the upper water column in the Indian sector of the Southern Ocean[J]. Earth and Planetary Science Letters, 1997, 147(1/4): 83-92.
[53]	Szymczak R, Waite T D. Generation and decay of hydrogen peroxide in estuarine waters[J]. Marine and Freshwater Research, 1988, 39(3): 289-299.
[54]	Kieber R J, Helz G R. Temporal and seasonal variations of hydrogen peroxide levels in estuarine waters[J]. Estuarine, Coastal and Shelf Science, 1995, 40(5): 495-503.
[55]	Yang Guipeng. Researches about photochemistry in ocean[J]. Marine Sciences, 1988, 6:51-55.
	[杨桂朋. 关于海洋光化学反应的研究[J]. 海洋科学, 1988, 6:51-55.]
[56]	Cooper W J, Zika R G. Photochemical formation of hydrogen peroxide in surface and ground waters exposed to sunlight[J]. Science, 1983, 220(4 598): 711-712.
[57]	Cooper W J, Zika R G, Petasne R G, et al. Photochemical formation of H2O2 in natural waters exposed to sunlight[J]. Environmental Science & Technology, 1988, 22(10): 1 156.
[58]	Scully N M, McQueen D J, Lean D R S, et al. Hydrogen peroxide formation: The interaction of ultraviolet radiation and dissolved organic carbon in lake waters along a 43°-75°N gradient[J]. Limnology and Oceanography, 1996, 41(3): 540-548.
[59]	O’Sullivan D W, Neale P J, Coffin R B, et al. Photochemical production of hydrogen peroxide and methylhydroperoxide in coastal waters[J]. Marine Chemistry, 2005, 97(1/2): 14-33.
[60]	Yocis B H, Kieber D J, Mopper K. Wavelength dependence of hydrogen peroxide photochemical production in Antarctic waters[J]. Antarctic Journal of the United States, 1995, 30(5): 146-147.
[61]	Wong A Y L, Wong G T F. The effect of spectral composition on the photochemical production of hydrogen peroxide in lake water[J]. Terrestrial Atmosphricand Oceanic Sciences, 2001, 12(4): 695-704.
[62]	Obernosterer I, Ruardij P, Herndl G J. Spatial and diurnal dynamics of Dissolved Organic Matter (DOM) fluorescence and H2O2 and the photochemical oxygen demand of surface water DOM acrossthe subtropical Atlantic Ocean[J]. Limnology and Oceanography, 2001, 46(3): 632-643.
[63]	Palenik B, Morel F M M. Amino acid utilization by marine phytoplankton: A novel mechanism[J]. Limnology and Oceanography, 1990, 35(2): 260-269.
[64]	Palenik B, Morel F M M. Comparison of cell-surface L-amino acid oxidases from several marine phytoplankton[J]. Marine Ecology Progress Series, 1990, 59:195-201.
[65]	Collén J, Rio M J, García-Reina G, et al. Photosynthetic production of hydrogen peroxide by Ulva rigida C. Ag.(Chlorophyta)[J]. Planta, 1995, 196(2): 225-230.
[66]	Navarro J A, Roncel M, De la Rosa F F, et al. Light-driven hydrogen peroxide production as a way to solar energy conversion[J]. Bioelectrochemistry and Bioenergetics, 1987, 18(1/3): 71-78.
[67]	Patterson C O, Myers J. Photosynthetic production of hydrogen peroxide by anacystis nidulans[J]. Plant Physiology, 1973, 51(1): 104.
[68]	Moffett J W, Zafiriou O C. An investigation of hydrogen peroxide chemistry in surface waters of vineyard sound with H218O2 and 18O2[J]. Limnology and Oceanography, 1990, 35(6): 1221-1229.
[69]	Palenik B, Zafiriou O C, Morel F M M. Hydrogen peroxide production by a marine phytoplankter[J]. Limnology and Oceanography, 1987, 32(6): 1365-1369.
[70]	Willey J D, Kieber R J, Lancaster R D. Coastal rainwater hydrogen peroxide: Concentration and deposition[J]. Journal of Atmospheric Chemistry, 1996, 25(2): 149-165.
[71]	Yuan J, Shiller A M. The variation of hydrogen peroxide in rainwater over the South and Central Atlantic Ocean[J]. Atmospheric Environment, 2000, 34(23): 3973-3980.
[72]	Thompson A M, Zafiriou O C. Air-sea fluxes of transient atmospheric species[J]. Journal of Geophysical Research, 1983, 88(C11): 6696-6708.
[73]	Wilson C L, Hinman N W, Sheridan R P. Hydrogen peroxide formation and decay in iron-rich geothermal waters: The relative roles of Abiotic and Biotic Mechanisms[J]. Photochemistry and Photobiology, 2000, 71(6): 691-699.
[74]	Moffett J W, Zafiriou O C. The photochemical decomposition of hydrogen peroxide in surface waters of the eastern Caribbean and Orinoco River[J]. Journal of Geophysical Research, 1993, 98(C2): 2307-2313.

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摘要

A review of the Study of Hydrogen Peroxide in Seawater