CDOM and its contribution to the underwater light climate of a shallow, microtidal estuary in south-western Australia

Light attenuation (K_d) of photosynthetically active radiation (PAR) by chromophoric dissolved organic matter (CDOM), total suspended solids (TSS) and chlorophyll a (Chl a) were measured at nine stations along an estuarine gradient in the Swan River, Western Australia, over 15 months. There were strong spatial gradients associated with the marine-freshwater transition along the 32 km of estuary sampled, as well as seasonal gradients mainly associated with rainfall, 80% of which occurs between May and September. CDOM absorbances at 440 nm reached a maximum of 10.9 m⁻¹ with the freshwater inflow but concentrations of suspended matter remained low throughout the sampling period (1.0–21.0 mg l⁻¹) under the diurnal tides of the estuary. CDOM was the dominant constituent of K_d and a stepwise multiple regression showed that 66% (p < 0.0001) of the variation in K_d can be explained by CDOM and an additional 8% (p < 0.0001) by TSS. As a consequence of this result, analysis into the influence of river discharge rates on CDOM absorbance levels was examined for 2002 using data collected during this study, and for 2000 and 2001 using historical dissolved organic carbon (DOC) and river discharge data. The outcome of this analysis infers that greater river discharge rates result in increased CDOM absorbances in the Swan River estuary.     

Release of dissolved organic matter during oxic and anoxic decomposition of salt marsh cordgrass

Chromophoric dissolved organic matter (CDOM), as the light absorbing fraction of bulk dissolved organic matter (DOM), plays a number of important roles in the global and local biogeochemical cycling of dissolved organic carbon (DOC) and in controlling the optical properties of estuarine and coastal waters. Intertidal areas such as salt marshes can contribute significant amounts of the CDOM that is exported to the ocean, but the processes controlling this CDOM source are not well understood. In this study, we investigate the production of DOM and CDOM from the decomposition of two salt marsh cordgrasses, Spartina patens, a C₄ grass, and Typha latifolia, a C₃ grass, in well-controlled laboratory experiments. During the seven-week incubation period of the salt marsh grasses in oxic and anoxic seawater, changes in dissolved organic carbon (DOC) concentrations, dissolved nitrogen (DN) concentrations, stable carbon isotopic composition of DOC (DOC-δ¹³C), and CDOM fluorescence demonstrate a significant contribution of DOC and CDOM to estuarine waters from salt marsh plants, such as Spartina and Typha species. In the natural environment, however, the release processes of CDOM from different cordgrass species could be controlled largely by the in situ oxic and anoxic conditions present during degradation which affects both the production and decomposition of DOC and CDOM, as well as the optical properties of CDOM in estuarine and coastal waters.     

海水有色可溶性有机物质荧光光谱的质量浓度响应

用自制的海水有色可溶性有机物(CDOM)干粉配制不同质量浓度的水溶液,研究其对三维荧光光谱(EEMS)和同步荧光光谱(SFS)的影响。结果表明:当CDOM质量浓度ρ≥62.5 mg/L时,其EEMS均为单一峰,随着质量浓度降低,激发和发射波长向短波长方向移动,这种波长移动变化与质量浓度的变化呈良好的线性相关关系;当ρ≤52.5 mg/L时,其三维荧光光谱显示3个峰。质量浓度在此范围内变化时,EEMS谱形基本不变。不同质量浓度CDOM水溶液的SFS显示,当质量浓度ρ≥150 mg/L时,随着质量浓度降低,激发和发射波长也向短波长方向移动,其谱形也发生变化;当ρ<150 mg/L时,激发和发射波长不发生漂移,谱形不变,荧光强度随质量浓度降低而降低。一定范围内CDOM质量浓度的变化会影响EEMS和SFS的谱形,从而影响EEMS和SFS法定性判定水体CDOM质量浓度的准确性。用EEMS和SFS法定性不同水体中的CDOM要考虑质量浓度的影响。     

九龙江口CDOM的荧光特性研究

利用荧光光度计对2001—2003年期间九龙江口4个航次水样中有色溶解有机物(CDOM)的荧光光谱进行了测定,并对其荧光性质、荧光强度的分布与季节性变化特征及其河口行为进行了分析,同时与厦门岛周边海域进行了比较。结果表明,输入九龙江口的CDOM荧光强度季节变化明显,夏高(17．16QSU)冬低(5．73QSU)。所有站位表层荧光强度明显高于底层,与河口区垂直分层一致。南支CDOM荧光强度随盐度的变化率高于北支,说明九龙江河水主要沿河口南岸入海。4个航次CDOM荧光强度都呈保守混合趋势,但观测到CDOM表观荧光效率随盐度增加而降低,暗示在低盐度区可能有胡敏酸的絮凝沉降。厦门周边海域CDOM荧光强度以西海域北部最高,西海域南部和同安湾次之,厦门东侧水道最低。各水域表层CDOM荧光强度与盐度均呈反相关关系,但不同水域回归曲线的斜率有差异,九龙江口、厦门西海域南部及厦门东侧水道三个海域具有同一相关趋势线,表明西海域南部和东侧水道主要受九龙江水输入控制,而西海域北部有不同的趋势线,这主要受污水输入的影响,由此很好地证卖了CDOM的水团示踪作用。     

海洋CDOM光吸收研究中若干问题的探讨

本文结合在厦门湾的现场调查和实验室分析，对目前海洋CDOM研究中的若干问题，从空白扣除、吸收系数和光谱斜率S值的估算方法、不同粒径滤膜对CDOM光学性质的影响等方面进行了探讨，并就河口混合过程中S值理论保守行为的判断进行了分析。结果表明，测定水样时，应以过滤后的纯水作为空白，CDOM的吸收系数应进行校正以消除样品中非CDOM信号的影响。进行CDOM的S值估算时，不论是高浓度的河流端还是低浓度的海端水样，当波长范围相同时，非线性回归所得S值均大于线性回归。当波长范围不同时，对任何一种回归方法，S值随长波区成分增多而降低，线性回归方法其降低程度尤其明显，总之波长范围对非线性回归处理的影响很小，S值通过对校正后的吸收系数进行非线性回归处理，同时波长范围选300—500nm较为适宜。决定河口混合时S值变化的因素不仅仅是河海两个端元CDOM的S值，还有它们CDOM浓度的相对大小，滤膜对近海Ⅱ类水域CDOM光吸收的影响是不可忽略的，以采用0．20μm左右的滤膜过滤水样为宜。     

Spatial and temporal distribution of chromophoric dissolved organic matter (CDOM) fluorescence and its contribution to light attenuation in UK waterbodies

Vertical attenuation of light through the water column (K_d) is attributable to the optically active components of phytoplankton, suspended particulate material (SPM) and chromophoric dissolved organic matter (CDOM). Of these, CDOM is not routinely monitored and was the main focus of this study. Concentrations and spatio-temporal patterns of CDOM fluorescence were investigated between August 2004 and March 2006, to quantify the correlation coefficient between CDOM and salinity and to better characterise the contribution of CDOM to K_d. Sampling was conducted at a broad range of UK and Republic of Ireland locations; these included more than 15 estuaries, 30 coastal and 70 offshore sites in the southern North Sea, Irish Sea, Liverpool Bay, Western Approaches and the English Channel.An instrument package was used; a logger with multi-sensor array was deployed vertically through the water column and concurrent water samples were taken to determine salinity, CDOM fluorescence and SPM. Surface CDOM fluorescence values ranged between 0.05 and 16.80 S.Fl.U. (standardised fluorescence units). A strong, negative correlation coefficient of CDOM to salinity (r² = 0.81) was found. CDOM absorption (aCDOM_λ) was derived from fluorescence measurements and was in the range 0.02–2.2 m⁻¹ with mean 0.15 m⁻¹. These results were comparable with direct measurements of aCDOM_λ in the same geographic regions, as published by other workers.Spatial differences in CDOM fluorescence were generally explicable by variation in salinity, in local conditions or catchment areas; e.g. CDOM at the freshwater end was 3.54–11.30 S.Fl.U., reflecting the variety of rivers sampled and their different catchments. Temporal changes in CDOM fluorescence were related to salinity. A significant and positive correlation was found between CDOM and K_d, and although CDOM was found to be less influential than SPM on K_d, it was still of significance particularly in coastal and offshore waters of lower turbidity.     

Concentration and Characterization of Colored Dissolved Organic Matter in the Surface Microlayer and Subsurface Water of the Yellow Sea and the East China Sea

The distribution and chemical properties of colored dissolved organic matter(CDOM) in the Yellow Sea and the East China Sea during December 2011-January 2012 were investigated. The input of freshwater and biological activities had an evident influence on the CDOM levels(characterized by the light absorption coefficient at the wavelength of 355 nm a₃₅₅) in the study area. The spatial distribution of CDOM levels displayed a gradually decreasing trend from the coastal waters(0.37 m^-1) to the open sea(0.18 m^-1). The spectral slope ratio(the slope ratio S_R defined as S_275-295:S_350-400) during the cruise was correlated with salinity, and exhibited a large variation from inshore(average of 2.515) to offshore sites(average of 5.327) compared with the distribution of a₃₅₅. The values of S_R were related to CDOM molecular weight(MW). The a₃₅₅, S_R, and chlorophyll a in 37 samples collected from the surface microlayer were significantly correlated with those in the corresponding subsurface water samples, implying a strong exchange action between the microlayer and bulk water. The a₃₅₅ and S_R of CDOM exhibited significant microlayer enrichment, with mean enrichment factors(EFs) of 1.72 and 1.62, respectively.     

Optical properties of chromophoric dissolved organic matter (CDOM) in surface and pore waters adjacent to an oil well in a southern California salt marsh

Chromophoric dissolved organic matter (CDOM) optical properties were measured in surface and pore waters as a function of depth and distance from an oil well in a southern California salt marsh. Higher fluorescence and absorbances in pore vs. surface waters suggest soil pore water is a reservoir of CDOM in the marsh. Protein-like fluorophores in pore waters at distinct depths corresponded to variations in sulfate depletion and Fe(II) concentrations from anaerobic microbial activity. These variations were supported by fluorescence indexes and are consistent with differences in optical molecular weight and aromaticity indicators. Fluorescence indices were consistent with autochthonous material of aquatic origin in surface waters, with more terrestrial, humified allochthonous material in deeper pore waters. CDOM optical properties were consistent with significantly enhanced microbial activity in regions closest to the oil well, along with a three-dimensional excitation/emission matrix fluorescence spectrum peak attributable to oil, suggesting anaerobic microbial degradation of oil.     

Variability of the apparent quantum efficiency of CO photoproduction in the Gulf of Maine and Northwest Atlantic

The photochemical oxidation of colored, dissolved organic matter (CDOM) is important for carbon cycling in the ocean. This oxidation process produces a number of products, including carbon monoxide (CO). While the photochemical production efficiency of CO (apparent quantum yield, AQY, defined in terms of CDOM absorbance) has been reported to be similar for many water types, a full evaluation of the observed natural variability in CO AQY requires additional study. Here we use a polychromatic irradiation system to determine twenty AQY spectra at sea on fresh samples ranging from the near coastal waters of the Gulf of Maine to the offshore waters of the Northwest Atlantic. Despite the geographic variability of these marine samples the AQY of CO production in the Gulf of Maine and Northwest Atlantic exhibited only a small degree of variability, none of which was not correlated with measured environmental parameters. Consequently, a single aggregate AQY spectrum _λ = e^{(−(9.134+0.0425(λ−290)))+e(−(11.316+0.0142(λ−290)))} was found to adequately represent the entire data set. Significantly, the accuracy of an AQY spectrum determined using this multispectral/statistical technique was confirmed with data obtained from a monochromatic irradiation technique on a single open ocean sample. Taken together, the AQY spectra determined in this study were similar in magnitude and shape to those previously published for marine samples and, overall, were somewhat lower than those previously reported for freshwater studies.