Dissolved copper and copper-organic complexes in the Narragansett Bay estuary

The geochemistry of dissolved copper-organic complexes was investigated in the estuarine waters of Narragansett Bay. A transect survey was conducted in August 1980, while one mid-bay station was monitored from March through August of that year. The transect data indicated that most of the copper-organic complexes enter the bay via sewage effluent which is discharged into the Providence River at the head of the bay. Organic copper concentrations in the estuary ranged from 0.12 to 2.30 μg kg^?1 and comprised from 14 to 70% of the total dissolved copper. The concentration of copper-organic complexes was not directly related to the amount of dissolved organic matter; and recently generated organic material from phytoplankton production within the bay had a negligible influence on the fraction of dissolved copper which was organically bound.The major source of total copper to the bay is anthropogenic inputs from sewage effluents. Particulate and dissolved copper concentrations ranged from 0.06 to 2.42 and 0.23 to 16.4 μg kg^?1, respectively, giving average values of about 40% particulate and 60% dissolved copper. Particulate copper concentrations decreased rapidly from the upper to the lower bay as a result of both removal and dilution. About 75% of the dissolved copper entering the bay is rapidly removed in the Providence River and upper bay, and the remaining portion (which is largely organic copper) follows conservative mixing in the mid to lower bay. The data suggest that copper binding by dissolved organic matter may be an important control on the riverine flux of dissolved copper through estuaries into coastal and oceanic waters.     

The effects of dissolved organic matter on the aqueous partitioning of polynuclear aromatic hydrocarbons

The partitioning of six polynuclear aromatic hydrocarbons into aqueous solutions containing dissolved organic matter from various coastal environments was investigated by liquid chromatography. Specific hydrocarbon-organic matter interactions were observed. The greatest interactions occurred with the very low solubility hydrocarbons and with organic matter of terrestrial origin. Ultrafiltration experiments suggested that it was the relatively high (greater than approximately 500) molecular weight organic matter that was interacting with the hydrocarbons.     

Seasonal Variations in Nutrient Budgets of Hakata Bay, Japan

Seasonal variations in freshwater, salt, phosphorus and nitrogen budgets of Hakata Bay, Japan were investigated from April 1993 until March 1994. The internal sink of dissolved inorganic phosphorus (DIP) and nitrogen (DIN), and the internal source of dissolved organic phosphorus (DOP) and nitrogen (DON) predominate in the bay. This means that the production of organic matter is larger than respiration, and atmospheric CO₂ is absorbed in the water column of Hakata Bay. Denitrification is more dominant than nitrogen fixation in the bay. Compared to Tokyo and Mikawa Bays, Hakata Bay is harder to eutrophicate, mainly due to the shorter residence time of freshwater.     

Features of winter sedimentation processes in Curonian Bay of the Baltic Sea

The concentration distribution was studied for dissolved oxygen, phosphorus forms, and particulate matter in Curonian Bay of the Baltic Sea in poorly known consolidated ice cover conditions during the winter seasons of 2010, 2011, and 2013. The surface and near-bottom waters were sampled at 51 stations. The ice cover exerts no significant effect on the typical seasonal variation of all considered parameters in the basin. The concentrations of mineral and organic phosphorus in the bay appeared to be lower by factors of 2–4 compared to summer values. A two- to threefold decrease in the concentrations of organic phosphorus since 2010 to 2011 and then to 2013 was recorded in the bay, which resulted from a decrease in phosphorus production by phytoplankton. Despite water being isolated from air by ice, the absence of wave mixing, and the decrease in oxygen production owing to the seasonal winter decrease in the intensity photosynthetic processes, no oxygen deficiency was found in the basin. This is because oxygen supplied to the bay by river runoff and production by photosynthesis in the bay exceed the utilization for oxidation of organic matter resulting from low bioproductivity of the waters during winter. The winter decrease in the fraction of biogenic particulate matter is seen as a four- to sevenfold drop in its total concentration in the waters compared to summer seasons. The absence of wave roiling of bottom sediments also caused a decrease in the secondary supply of biogenic particulate matter from sediments into near-bottom waters. No negative trends of geoecological conditions in the bay were revealed by the studied parameters under consolidated ice cover conditions.     

Coastal environmental assessment and management by ecological simulation in Yeoja Bay, Korea

An eco-hydrodynamic model was used to estimate the carrying capacity of pollutant loads and response of water quality to environmental change in Yeoja Bay, Korea. An energy-system model also was used to simulate the fluctuation in nutrients and organic matter in the bordering wetland. Most water quality factors showed a pulsed pattern, and the concentrations of nutrients and organic matter of seawater increased when input loads of nutrients increased due to freshwater discharge. The well-developed tidal zones and wetlands in the northern area of the bay were highly sensitive to input loads. Residence times of water, chemical oxygen demand (COD), and dissolved inorganic nitrogen (DIN) within the bay were estimated to be about 16 days, 43.2 days, and 50.2 days, respectively. Water quality reacted more sensitively to the effects of nitrogen and phosphorus input than to COD. A plan to reduce the present levels of COD and dissolved inorganic phosphorus (DIP) by 20–30% and DIN by at least 50% in pollutant loads is needed for satisfying the target water quality criteria. The natural removal rate of nutrients in wetlands by reeds was assessed to be approximately 10%.     

夏季大亚湾悬浮颗粒有机物碳、氮同位素组成及其物源指示

2015年夏季开展了大亚湾悬浮颗粒有机物碳（POC）、氮含量（PN）及其同位素组成的研究,结果表明,δ13C_POC和δ15N_PN的变化范围分别为-25.7‰~-17.4‰和-6.3‰~10.4‰,平均值分别为-20.2‰和8.2‰。大亚湾悬浮颗粒有机物含量及其碳氮同位素组成的空间变化反映了不同有机质来源的影响:喜洲岛附近海域表现出高POC、PN、δ13C_POC和δ15N_PN的特征,指征着浮游植物水华的主导贡献;东北部范和港附近海域具有高POC、PN、低δ13C_POC和高δ15N_PN的特征,反映了河流/河口水生有机物的影响;湾顶白寿湾附近海域的δ13C_POC和δ15N_PN出现低值,体现了陆源有机质和人类污水排放的影响。借助δ13C_POC和δ15N_PN的三端元混合模型,定量出海洋自生有机质、陆源有机质、河流/河口水生有机质等3个来源的贡献平均分别为70%、13%和17%,其中海洋自生有机质是夏季大亚湾悬浮颗粒有机物的最主要来源。从这3种来源颗粒有机物含量的空间变化看,海洋自生有机质含量由湾内向湾外减少,与初级生产力的空间变化相对应;河流/河口水生有机质含量在大亚湾东北部出现高值;陆源有机质含量在表、底层出现不同态势,表层陆源有机物含量在湾中部海域最低,而底层则呈现出自湾内向湾口增加的趋势,主要受控于离岸距离和珠江冲淡水、粤东沿岸上升流输送的影响。     

Chemical and GC-MS characterization of marine dissolved lipids

The chloroform-extractable ‘lipid’ fraction of dissolved organic matter in seawater was analyzed by gravimetry, liquid chromatography, gas chromatography (GC), and gas chromatography—mass spectrometry (GC—MS). Gravimetric concentrations of dissolved lipids in the Gulf of Mexico were in the range of 60–160 μg 1^?1 in near-surface waters and 61–116 μg 1^?1 in near bottom waters and accounted for ～4% of the dissolved organic carbon. Over a 12-h sampling period and a 5-d sampling period extensive variability in dissolved lipid quantity and quality were observed. The major percentage of extractable weight was collected in the polar liquid chromatographic fraction (55–95%). Gas chromatographic concentrations of the aliphatic fractions were in the range of 0.014-0.187 μg 1^?1. Concentrations derived from gas chromatography were consistently lower than gravimetrically-derived concentrations. A number of compounds were tentatively identified by a combination of GC, GC—MS, and authentic standards. The major components of the analyzable dissolved lipids were n-alkanes (C₁₆C₃₂), pristane, phytane, methyl, ethyl and propyl esters of fatty acids. Minor components included olefins and cycloalkanes, aromatics, short-chained acids, and possibly a lactone and an alcohol. All concentrations and compounds were indicative of a fairly pristine environment. The n-alkane distribution appears to be the result of marine and terrestrial inputs superimposed on a chronic low-level background of oil pollution. It is suggested that the fatty acid esters and other fragment molecules are the résult of the degradation of humic substances. A number of potential indicators of source were isolated.     

Chemical studies of copper-organic complexes isolated from estuarine waters using C18 reverse-phase liquid chromatography

Dissolved organic matter (DOM) and dissolved copper-organic complexes were isolated from the estuarine waters of Narragansett Bay, RI, using reverse-phase liquid chromatography employing C₁₈ Sep-Pak cartridges (Waters Associates). The cartridges were found to have a constant retention efficiency for processing ? 1-l volumes of seawater. Fractionation of the isolated material, by sequential elution of the Sep-Pak with water: methanol mixtures of increasing organic solvent concentration, yielded a fraction of the organic matter with a specific copper activity six times greater than the overall activity for the isolated DOM. Analysis of this fraction by high performance liquid chromatography suggested that the organic components are of intermediate polarity and have appreciable aromatic character.An investigation of the protonation characteristics of the isolated complexes indicated that most of the copper is associated with a broad range of acidic sites on the DOM. Analysis by electron paramagnetic resonance spectroscopy confirmed the organic association of the isolated copper and also suggested the presence of several types of binding sites which probably involve oxygen donor ligands.Studies of the exchange of ⁶⁴Cu with these binding sites on the isolated DOM indicated that 70% of the sites undergo rapid exchange with copper in seawater while 20% of these sites did not exchange in a 24-h time period.     

Tracing origins of sewage and organic matter using dissolved sterols in Masan and Haengam Bay,Korea

Masan and Haengam Bays in Korea are highly polluted and semi-enclosed. Domestic and industrial effluents are directly or indirectly discharged into the bays through sewage treatment plants (STP) and creeks. In this study, 15 dissolved sterol compounds were determined in order to understand their sources and relative contribution. Freshwater samples were taken from 13 creeks and at two STP sites on a monthly basis. Total dissolved sterol concentrations ranged from 993 to 4158 ng/L. The concentrations of sterols in winter were higher than in summer. Among the sterols analyzed, cholesterol, β-sitosterol, coprostanol and cholestanone were major compounds in creek water. Seawater samples were concurrently collected at 21 stations in Masan Bay. Total sterol concentrations ranged 118–6,956 ng/L. Inner bay showed high concentrations of sterols in summer, while outer bay showed high sterol concentrations in winter. Among the sterols, cholesterol, β-sitosterol and brassicasterol were major compounds in seawater. In order to examine the contribution of urban sewage, the concentration of coprostanol and fecal sterol ratios were calculated. Most of the creek water, inner bay and near STP outlet samples were affected by sewage. Terrestrial organic matters accounted for a high proportion of dissolved organic matter origin. Fecal origins were relatively high in the inner bay areas and in the STP outlet, while sterols of marine origin were high in the outer bay areas.     

胶州湾沉积物中氨基酸对有机质降解及细菌源贡献的指示作用解析

基于对胶州湾表层沉积物中总可水解氨基酸（THAA）的含量、组成、构型及分布特征的系统研究,通过氨基酸碳氮归一化产率（THAA-C%,THAA-N%）、降解因子DI、反应活性指数RI以及D型氨基酸占比（D-AA%,摩尔百分比）等指标结合碳氮比（TOC/TN）、碳稳定同位素（δ13C）探析了胶州湾沉积物中有机质的来源与降解状态,利用细菌源有机质及胞外肽酶活性（EEA）探讨了微生物在有机质迁移转化过程中的作用与贡献。结果表明,胶州湾表层沉积物中氨基酸平均含量为（7.60±3.64）μmol/g,在陆源与海源混合影响下,其水平分布呈现湾内高于湾外、湾内东部高于西部的特点,表明湾内东部陆源输入对沉积物THAA具有较高贡献。THAA-C%、THAA-N%、DI、RI以及D-AA%等指示因子均显示胶州湾表层沉积物中有机质的降解程度呈现湾外高于湾内、湾内东部高于西部的变化趋势,有机质来源、微生物活性与上覆水水深共同影响了有机质的降解程度。胶州湾表层沉积物中细菌源有机碳的贡献率为（29.35±18.73）%,其水平分布显示出湾内西部与湾外相近且高于湾内东部的特点。细菌胞外肽酶活性（EEA）平均为（0.81±1.31）nmol/（g·h）（以MCA计）,整体分布趋势与细菌贡献率相反,呈现湾内东部高于湾内西部和湾外的特性。沉积物中有机质的不同海源、陆源占比决定了有机质的可降解性,而有机质的降解程度进一步影响了细菌源有机质的贡献与胞外肽酶活性。     

Chemical and GC-MS characterization of marine particulate lipids

The lipid fraction of particulate organic matter in seawater was analyzed by gravimetry, liquid chromatography, gas chromatography (GS), and gas chromatography—mass spectrometry (GS—MS). Gravimetric concentrations in the Gulf of Mexico were in the range of 12–70 μg 1^?1 for near-surface samples and 9–52 μg 1^?1 for near-bottom samples. The lipids accounted for ～20% of the particulate organic carbon. Particulate lipids were found to be a much more complex mixture of organic compounds than the dissolved lipids and their composition was much more variable. The majority of the extracted weight was recovered in the polar liquid chromatography fraction (49–85%). The major components of the analyzable particulate lipids were similar to those of the dissolved lipids, namely, n-alkanes, pristane, phytane, and methyl, ethyl and propyl fatty acid esters. Often olefins, alkylated benzenes, quinones, and the unresolved GC area contribute a substantial part to the total particulate lipids. Minor components included ketones, phenols, indanes, acids, benzoates, aromatics and possibly derivatives of inositol, dioxane, and pyran. The low concentrations observed confirm that the area is relatively pristine though some evidence for chronic low-level oil pollution was present. Seasonal, diurnal, vertical and areal variations were observed in the particulate lipids. Lipid concentrations not only decreased with depth but they were also a decreased percentage of the organic carbon present. This may indicate the loss of labile carbon with depth due to reworking in the euphotic zone. Anoxic conditions appeared to promote the preservation of lipid materials in the particulate phase, n-Alkanes and fatty acid esters were common to both the particulate and dissolved phases and had similar distributions.     

Short-term variation in behavior of allochthonous particulate organic matter accompanying changes of river discharge in Ise Bay,Japan

The composition and behavior of allochthonous particulate organic matter (POM) in the northern part of Ise Bay, Japan were investigated to elucidate the short-term variation in POM accompanying changes in river discharge. The behavior of POM was significantly regulated by hydrographic conditions, but behavior was different in the upper layer versus the middle and lower layers. The former showed simple dynamics controlled by the river plume, while the latter showed complex dynamics because of changes in river discharge and subsequent variation in estuarine circulation. During normal discharge, the contribution of riverine materials to POC in the surface water within the bay was negligible because most riverine organic matter is deposited before flowing into the bay. During high discharge, on the other hand, the contribution of riverine organic matter to total POM increased to 50% at ∼10 km from the river mouth. Though riverine organic matter loads increased, the total amount of POC decreased around the river mouth due to flushing of phytoplankton. After river discharge, the contribution decreased rapidly.The behavior of POM in the middle and lower layers differed from that in the surface layer. At normal discharge, the influence of riverine organic matter was weak. During high discharge, high flooding temporarily weakened the bottom inflow, resulting in heavier riverine organic matter distributed from the river mouth to mid regions within the bay in the lower layer. The maximum contribution of riverine organic matter to total POM was estimated to be ∼60% around 25 km from the river mouth. After high discharge, riverine POM in the lower layer was pushed to the bay head by enhanced estuarine circulation and was uplifted to the middle layer. The behavior of riverine POM dynamically changed in relation to river discharge, and exerted a significant influence on bottom water conditions in the bay.     

Biogeochemical studies in the sea

My studies on metabolism of organic matter in aquatic environments first involved research on the sedimentation process of organic matter in lacustrine environments. Subsequently, measurements of primary production in lake and sea water were undertaken to know the organic substance supply into the metabolism. After establishing the routine technique of productivity measurement in aquatic environment, the primary production and the photosynthetic characteristics in waters in the northwestern Pacific, the western Indian Ocean and the Antarctic Sea were studied. Following the development of new methods to determine the organic substances in the dissolved and particulate forms and chlorophyll pigment in seawater, their distributions both horizontal and vertical directions were determined. And I have had interest in the mechanism producing a subsurface chlorophyll maximum in the ocean. Recently, my major interest has been directed to the coastal waters. The nitrogen cycle was studied in oyster beds and the research on eutrophication processes in a shallow bay is being carried out from the aspect of production and decomposition of organic matter.     

Metaproteomic characterization of dissolved organic matter in coastal seawater

We performed a comprehensive metaproteomic analysis of the dissolved organic matter (DOM) in Japanese coastal waters using liquid chromatography–tandem mass spectrometry and demonstrated that these proteomes were characterized by proteins with various functions, including metabolic enzymes, membranes, and photosynthetic proteins. The protein sources included cyanobacteria, heterotrophic bacteria, and eukaryotic phytoplankton. Most of the components were similar among samples and also similar to pelagic components. We also observed differences in the compositions of the microbial communities of origin among the different dissolved protein samples and differences in the relative abundance of specific dissolved protein types (e.g., cytoskeletal proteins), possibly indicating potential dynamics in the coastal DOM pool.     

The distribution and flux of particulate matter in the Bideford River Estuary,Prince Edward Island,Canada

The temporal and spatial distribution of total and organic particulate matter is investigated in the Bideford River estuary. Particulate matter is homogenously distributed in both the water column and the surface sediment, due to high rates of resuspension and lateral transport. The measured mean sedimentation rate for the estuary is 183·5 g of particulate matter m^?2 day^?1, of which more than half is due to resuspension.The surface sediment of the estuary is quantitatively the dominant reservoir of organic matter, with an average of 902·5 g of particulate organic carbon (POC) m^?2 and 119·5 g of particulate organic nitrogen (PON) m^?2. Per unit surface area, the sediment contains 450 times more POC and 400 times more PON than the water column. Terrestrial erosion contributes high levels of particulate matter, both organic and inorganic, to the estuary from the surrounding watershed. Low rates of sediment export from the estuary result in the accumulation of the terrigenous material. The allochthonous input of terrigenous organic matter masks any relationship between the indigenous plant biomass and the organic matter.In the water column, a direct correlation exists between the organic matter, i.e. POC and PON, concentration and the phytoplankton biomass as measured by the plant pigments. Resuspension is responsible for the residual organic matter in the water column unaccounted for by the phytoplankton biomass.The particulate content of the water column and the surface sediment of the estuary is compared to that of the adjacent bay. Water-borne particulate matter is exported from the estuary to the bay, so that no significant differences in concentration are noted. The estuarine sediment, however, is five to six times richer in organic and silt-clay content than the bay sediment. Since sediment flux out of the estuary is restricted, the allochthonous contribution of terrigenous particulate matter to the bay sediment is minor, and the organic content of the bay sediment is directly correlated to the autochthonous plant biomass.     

春、秋季考洲洋海水质量状况及评价方法初探

文章利用2017年11月（秋季）和2018年4月（春季）对惠州考洲洋海域开展的两个航次水环境调查数据,分析了考洲洋海域表层溶解氧（DO）、化学需氧量(COD)、无机氮(DIN)、无机磷(DIP)和石油类（OIL）等典型水质因子的水平分布和季节变化情况。结果表明,秋季溶解氧、化学需氧量、石油类分别在盐洲岛以东附近海域、考洲洋湾顶海域和盐洲岛东南海域出现高值区,而无机氮在整个考洲洋无明显区域分布差异,无机磷含量呈现考洲洋内湾到湾口逐渐递减的趋势;春季化学需氧量、无机磷均在考洲洋湾顶出现高值区域,无机氮在盐洲岛以东附近海域出现高值区,而溶解氧和石油类无明显变化。从季节变化来看,秋季考洲洋海域溶解氧、化学需氧量和石油类平均含量均比春季高;无机氮、无机磷则相反,平均含量秋季低于春季。同时,文章还分别利用单因子和综合因子方法对海水有机污染状况进行评价并对其进行比较分析,结果表明,有机污染评价指数法可充分考虑多种水质因子,更适合对考洲洋水环境质量进行评价,得到较为客观的综合评价结果。     

胶州湾海水中悬浮体的分布及其季节变化

海水中的悬浮体包含有机物和无机物,有机物主要为有机碎屑颗粒,例如植物碎屑、浮游生物等;无机物主要是无机碎屑矿物、粘土矿物,也有少量硅质生物骨骼。海水中无机颗粒物质能通过吸附作用,从海水中有效地富集有机溶解物质。海水中天然有机物的分布、变化与浮游生物的活动密切相关,在海洋食物链中占有重要地位,海水中的颗粒有机物是某些游泳动物和底栖动物的食物,因此,海水中有机物的存在不仅对海洋生物有一定的生态学意义,而且对海洋无机元素的存在形式和地球化学转移过程都有直接影响。 胶州湾是一个典型的半封闭海湾,平均水深7m,面积390km2,自然环境优良,水产资源丰富,因此胶州湾的生态环境、生物资源及生态系统持续发展的研究对胶州湾的综合开发利用具有十分重要的意义。胶州湾海水中悬浮体的分布与变化是胶州湾生态环境研究中的一个重要组成部分。本文根据胶州湾海水中悬浮体的定点观测资料,阐明了胶州湾海水中悬浮体平均含量的分布及其季节变化特征,分析了影响悬浮体含量变化的主要因素。     

Composition of the organic matter of the water,suspended matter,and bottom sediments in Nha Trang Bay in Vietnam in the South China Sea

Research has been conducted in Nha Trang Bay (Southern Vietnam, the South China Sea) at the section from the estuary of the Cai River to the marine part of the bay, as well as in the area of coral reefs. The objects of the studies are the river and sea waters, the suspended matter, and the bottom sediments. Data on the dissolved organic carbon and the total nitrogen in the water are obtained. The organic carbon content is estimated in the suspended matter; the organic carbon and the molecular and group composition of the n-alkanes are determined in the bottom sediments. The molecular and group composition of the n-alkanes in the bottom sediments of the landfill have made it possible to identify three types of organic matter (OM): marine, mixed, and of mainly terrigenous origin. All the types of OM are closely related to the specificity of the sedimentation and the hydrodynamics of the waters in this water area.     

Chromatographic studies of dissolved organic matter and copper-organic complexes isolated from estuarine waters

Dissolved organic matter (DOM) and dissolved copper-organic complexes were isolated from the estuarine waters of Narragansett Bay, RI, using reverse-phase liquid chromatography (RPLC). Different types of reverse-phase BOND ELUT columns (Analytichem International), including C₂, C₁₈ and phenyl-bonded phases, were studied to determine their adsorption efficiency for extracting DOM. Extraction efficiencies followed the order phenyl > C₁₈ > C₂, and phenyl − C₁₈ > C₂ for DOM and organic copper, respectively. However, comparisons of BOND ELUT and C₁₈ SEP-PAK (Waters Associates) columns indicated that SEP-PAK columns were the most efficient when both DOM and organic copper were considered. Chromatographic profiles of the isolated DOM obtained using high-performance liquid chromatography were similar in elution characteristics and resembled chromatograms typical of fulvic acid. The UV-absorption characteristics of the DOM showed small differences and suggested that the different reverse-phase columns isolated material that was qualitatively similar.Copper-organic complexes isolated using C₁₈ RPLC were studied to examine the dissociation of organically bound copper in seawater as the pH is lowered. Only a small amount of the complexed copper was displaced by the H⁺ with about 40% of the copper remaining bound at pH 3. However, the chromatographic elution behavior of the DOM and organic copper was significantly altered under acidic conditions as a result of protonation of acidic functional sites on the organic matter.     

厦门潘涂虾池及其附近内湾各态氮的季节性变化特征

1996年6月至1997年2月，对厦门市潘涂垦区两口虾池及附近内湾不同形态氮的含量与动态进行调查。结果显示虾池的可溶性有机氮（DON）含量明显高于邻近内湾，颗粒有机氮（PN）多数时间也高于内湾，而邻近内湾可溶性无机氮（DIN）含量则明显比池内的高。虾池中的氮主要以DON形态存在（59．76％），DIN，PN含量较少（9．37％和20．87％）；邻近内湾则是以DIN为主（59．97％），其次为DON（29．55％），PN所占比例最小（10．48％）。吓池与邻近内湾不同形态氮的季节变化也存在一定差异。