Concentrations of alkyphenol polyethoxylates entering UK estuaries

Concentrations of the weakly oestrogenic degradation products of alkylphenol polyethoxylate (APE) surfactants (nonylphenol, octylphenol, nonylphenol monoethoxylate and nonylphenol diethoxylate) were measured in water and sediments from British rivers and estuaries collected during 1994 and 1995. In addition, a series of samples of tissues of wild fish from the River Aire, and from a laboratory dosing experiment were analysed for alkylphenols, to assess the degree of bioaccumulation of these compounds. Measurable concentrations of APE residues were recorded in the River Aire (15–76 μg/l total extractable alkylphenols), the River Mersey (6–11 μg/l) and the Tees estuary (up to 76 μg/l). These levels exceed, or are close to, the no observed effect concentration for the induction of vitellogenesis in caged trout (5–20 μg/l total extractable alkylphenols), and may be sufficient to exert an oestrogenic effect on fish populations in these areas. A sediment sample from Bingley on the River Aire contained 15 μg/g (dry weight) nonylphenol, and concentrations in sediments from the Tees and Mersey estuaries exceeded 1 μg/g. These rivers receive a variety of trade waters via sewage treatment works (STW) effluents containing significant concentrations of APE. Elsewhere, concentrations in water and sediments were near or below limits of detection and biological effects are unlikely, suggesting that any oestrogenic effects observed in sewage outfalls and rivers not directly impacted by APE-containing trade-waters may be caused by other chemicals. Analysis of samples of trout muscle taken from a tank dosed at 65 μg/l nonylphenol indicated a bioaccumulation factor of between 90 and 125 after 3 weeks exposure. Samples of wild fish from the River Aire contained up to 0.8 μg/g nonylphenol in the muscle, a tissue bioaccumulation factor of approximately 50 relative to measured concentrations in water samples. A series of fish samples taken from offshore for food quality assurance purposes contained no detectable levels of APE residues (0.05–0.1 μg/g nonylphenol).

On-line voltammetric monitoring of dissolved Cu and Ni in the Gulf of Cadiz, south-west Spain

Geochemical processes in estuarine and coastal waters often occur on temporally and spatially small scales, resulting in variability of metal speciation and dissolved concentrations. Thus, surveys, which are aimed to improve our understanding of metal behaviour in such systems, benefit from high-resolution, interactive sampling campaigns. The present paper discusses a high-resolution approach to coastal monitoring, with the application of an automated voltammetric metal analyser for on-line measurements of dissolved trace metals in the Gulf of Cadiz, south-west Spain. This coastal sea receives metal-rich inputs from a metalliferous mining area, mainly via the Huelva estuary. On-line measurements of dissolved Cu, Zn, Ni and Co were carried out on-board ship during an eight-day sampling campaign in the study area in June 1997. A pumping system operated continuously underway and provided sampled water from a depth of ca. 4 m. Total dissolved metal concentrations measured on-line in the Gulf of Cadiz ranged between <5 nM Cu (<3 nM Ni) ca. 50 km off-shore and 60–90 nM Cu (5–13 nM Ni) in the vicinity of the Huelva estuary. The survey revealed steep gradients and strong tidal variability in the dissolved metal plume extending from the Huelva estuary into the Gulf of Cadiz. Further on-line measurements were carried out with the automatic metal monitor from the bank of the Odiel estuary over a full tidal cycle, at dissolved metal concentrations in the μM range. The application confirmed the suitability of the automated metal monitor for coastal sampling, and demonstrated its adaptability to a wide range of environmental conditions in the dynamic waters of estuaries and coastal seas. The near-real time acquisition of dissolved metal concentrations at high resolution enabled an interactive sampling campaign and therefore the close investigation of tidal variability in the development of the Huelva estuary metal plume.

Validation and in situ application of an automated dissolved nickel monitor for estuarine studies

The validation of a fully automated dissolved Ni monitor for in situ estuarine studies is presented, based on adsorptive cathodic stripping voltammetry (AdCSV). Dissolved Ni concentrations were determined following on-line filtration and UV digestion, and addition of an AdCSV ligand (dimethyl glyoxime) and pH buffer (N-2-hydroxyethylpiperazine-N′-2-ethanesulphonic acid). The technique is capable of up to six fully quantified Ni measurements per hour. The automated in situ methodology was applied successfully during two surveys on the Tamar estuary (south west Britain). The strongly varying sample matrix encountered in the estuarine system did not present analytical interferences, and each sample was quantified using internal standard additions. Up to 37 Ni measurements were performed during each survey, which involved 13 h of continuous sampling and analysis. The high resolution data from the winter and summer tidal cycle studies allowed a thorough interpretation of the biogeochemical processes in the studied estuarine system.

Interference effects in the extraction of trace metals from estuarine waters

We have found that a commonly used complexation and solvent extraction technique (using mixed dithiocarbamates/Freon/HNO3) does not always extract Cd, Co, Cu and Ni from estuarine samples with the same efficiency as from Milli-Q water. For samples collected from the Derwent Estuary (Australia), the reduced extraction efficiency only occurred for unfiltered samples, but low extraction efficiencies were also observed for a (filtered) riverine certified reference material (SLRS-3) suggesting that the effect may be widespread. We have not been able to identify the reason for the low extraction efficiency and, although it is strongly correlated with the presence of high concentrations of suspended solids, dissolved organic matter and particulate iron, we have no experimental evidence to directly link any of these parameters to the effect. It is possible that similar effects may occur in other techniques which rely on a preconcentration step prior to analysis and that some literature values of heavy metals in estuarine waters may be low. We propose a modification of the standard complexation/solvent extraction method which overcomes these difficulties without adding significantly to the time taken for analyses.

Quantitatively distinguishing sediments from the Yangtze River and the Yellow River using delta Eu-N-I REEs pound plot

Sediment samples were collected from the lower channel of the Yangtze River and the Yellow River and the contents of rare earth elements (REEs) were measured. In addition, some historical REEs data were collected from published literatures. Based on the delta Eu-N-I REEs pound plot, a clear boundary was found between the sediments from the two rivers. The boundary can be described as an orthogonal polynomial equation by ordinary linear regression with sediments from the Yangtze River located above the curve and sediments from the Yellow River located below the curve. To validate this method, the REEs contents of sediments collected from the estuaries of the Yangtze River and the Yellow River were measured. In addition, the REEs data of sediment Core 255 from the Yangtze River and Core YA01 from the Yellow River were collected. Results show that the samples from the Yangtze River estuary and Core 255 almost are above the curve and most samples from the Yellow River estuary and Core YA01 are below the curve in the delta Eu-N-I REEs pound plot. The plot and the regression equation can be used to distinguish sediments from the Yangtze River and the Yellow River intuitively and quantitatively, and to trace the sediment provenance of the eastern seas of China. The difference between the sediments from two rivers in the delta Eu-N-I REEs pound plot is caused by different mineral compositions and regional climate patterns of the source areas. The relationship between delta Eu-N and I REEs pound is changed little during the transport from the source area to the river, and from river to the sea. Thus the original information on mineral compositions and climate of the source area was preserved.

The change of characteristics of tidal wave in the Changjiang River mouth area since the post-glacial transgression maximum

During the period of the post-glacial transgression maximum (PGTM), there was a huge trumpet estuary in the modern Changjiang River Delta area. The location and the shape of the Paleo-Changjiang River Estuary (PCRE) were much different from those of the present Changjiang River Estuary. The study on the change of characteristics of tidal wave in the Changjiang River mouth area since the PGTM can help to understand better the dynamic development of the Changjiang River Delta. The course curves of tidal level and tidal current velocity during a single tidal cycle for 35 points are calculated, and characteristics of tidal waves in the PCRE and its adjacent area are compared with those of tidal waves in the modern Changjiang River mouth area. The results show that the tidal waves within the PCRE and in its adjacent area during the period of the PGTM belonged to standing wave or a mixture of standing wave and progressive wave. Since then, the tidal wave in the Changjiang River mouth become gradually to be progressive wave with the PCRE being filled and the Changjiang River mouth shifting southeastwards.

Response of coastal marine eco-environment to river fluxes into the sea: A case study of the Huanghe (Yellow) River mouth and adjacent waters

The impact of the Huanghe (Yellow) River outflows on its estuary was investigated with river gauging and shipboard hydrographic observations. The river flux has been decreasing dramatically; the discharges of water and sediment in the 1990s dropped to 27.4% and 31.9% of those in the 1950s, respectively, resulting in frequent and lengthy events of downstream channel dry-up since the 1970s. There were accumulatively 897 zero-flow days during the 1990s in the river course below the Lijin Hydrological Station, 100 km upstream from the river mouth, which is 82.4% of that in 1972. As freshwater input decreases, river-borne nutrients to the estuarine increased significantly. Concentration of dissolved inorganic nitrogen (DIN) in the 1990s was four times of that in 1950s. Changes in amount and content of the riverine inputs have greatly affected the estuarine ecosystem. Over the past several decades, sea surface temperature and salinity in the estuary and its adjacent waters increased and their distribution pattern altered in response to the reduction of freshwater inflow. The distribution of and seasonal succession in nutrient concentrations in the surface layer have also changed with a shift of river outlet and the decrease in riverine nutrient loads. Furthermore, deterioration of estuarine ecosystem by less river input has decreased primary productivity in the deltaic region waters, and in turn depressed the fishery. (C) 2008 Published by Elsevier Ltd.

Flux and fate of Yangtze river sediment delivered to the East China Sea

Numerous cores and dating show the Yangtze River has accumulated about 1.16 x 10(12) t sediment in its delta plain and proximal subaqueous delta during Holocene. High-resolution seismic profiling and coring in the southern East China Sea during 2003 and 2004 cruises has revealed an elongated (similar to 800 km) distal subaqueous mud wedge extending from the Yangtze River mouth southward off the Zhejiang and Fujian coasts into the Taiwan Strait. Overlying what appears to be a transgressive sand layer, this distal clinoform thins offshore, from similar to 40 in thickness between the 20 and 30 m water depth to < 1-2 in between 60 and 90 m water depth, corresponding to an across shelf distance of less than 100 km. Total volume of this distal mud wedge is about 4.5 x 10(11) m(3), equivalent to similar to 5.4 x 10(11) t of sediment. Most of the sediment in this mud wedge comes from the Yangtze River, with some input presumably coming from local smaller rivers. Thus, the total Yangtze-derived sediments accumulated in its deltaic system and East China Sea inner shelf have amounted to about 1.7 x 10(12) t. Preliminary analyses suggest this longshore and across-shelf transported clinoform mainly formed in the past 7000 yrs after postglacial sea level reached its mid-Holocene highstand, and after re-intensification of the Chinese longshore current system. Sedimentation accumulation apparently increased around 2000 yrs BP, reflecting the evolution of the Yangtze estuary and increased land erosion due to human activities, such as fanning and deforestation. The southward-flowing China Coastal Current, the northward-flowing Taiwan Warm Current, and the Kuroshio Current appear to have played critical roles in transporting and trapping most of Yangtze-derived materials in the inner shelf, and hence preventing the sediment escape into the deep ocean. (c) 2006 Elsevier B.V. All rights reserved.

Contrasting chemical and isotopic compositions of organic matter in Changjiang (Yangtze river) estuarine and East China Sea shelf sediments

To examine the source and preservation of organic matter in the shelf sediments of the East China Sea (ECS), we measured bulk C/N and isotopes, organic biomarkers (n-alkanes and fatty acids) and compound-specific (fatty acids) stable carbon isotope ratios in three sediment cores collected from two sites near the Changjiang Estuary and one in the ECS shelf. Contrasting chemical and isotopic compositions of organic matter were observed between the estuarine and shelf sediments. The concentrations of total n-alkanes and fatty acids in the shelf surface sediments (0-2 cm) were 5-10 times higher than those in estuarine surface sediments but they all decreased rapidly to comparable levels below the surface layer. The compositions of n-alkanes in the estuarine sediments were dominated by C-26-C-33 long-chain n-alkanes with a strong odd-to-even carbon number predominance. In contrast, the composition of n-alkanes in the shelf sediment was dominated by nC(15) to nC(22) compounds. Long-chain (> C-20) fatty acids (terrestrial biomarkers) accounted for a significantly higher fraction in the estuarine sediments compared to that in the shelf sediment, while short-chain (< C-20) saturated and unsaturated fatty acids were more abundant in the shelf surface sediments than in the estuarine sediments. Stable carbon isotopic ratios of individual fatty acids showed a general positive shift from estuarine to shelf sediments, consistent with the variations in bulk delta(CTOCTOC)-C-13. These contrasts between the estuarine and shelf sediments indicate that terrestrial organic matter was mainly deposited within the Changjiang Estuary and inner shelf of ECS. Post-depositional diagenetic processes in the surface sediments rapidly altered the chemical compositions and control the preservation of organic matter in the region.

Preservation of black carbon in the shelf sediments of the East China Sea

Concentrations and carbon isotopic (C-14, C-13) compositions of black carbon (BC) were measured for three sediment cores collected from the Changjiang River estuary and the shelf of the East China Sea. BC concentrations ranged from 0.02 to 0.14 mg/g (dry weight), and accounted for 5% to 26% of the sedimentary total organic carbon (TOC) pool. Among the three sediment cores collected at each site, sediment from the Changjiang River estuary had relatively high BC contents compared with the sediments from the East China Sea shelf, suggesting that the Changjiang River discharge played an important role in the delivery of BC to the coastal region. Radiocarbon measurements indicate that the ages of BC are in the range of 6910 to 12250 years old B. P. (before present), that is in general, 3700 to 9000 years older than the C-14 ages of TOC in the sediments. These variable radiocarbon ages suggest that the BC preserved in the sediments was derived from the products of both biomass fire and fossil fuel combustion, as well as from ancient rock weathering. Based on an isotopic mass balance model, we calculated that fossil fuel combustion contributed most (60%. 80%) of the BC preserved in these sediments and varied with depth and locations. The deposition and burial of this "slow-cycling" BC in the sediments of the East China Sea shelf represent a significant pool of carbon sink and could greatly influence carbon cycling in the region.

Paleoenvironmental change in the middle Okinawa Trough since the last deglaciation: Evidence from the sedimentation rate and planktonic foraminiferal record

Well-dated, high-resolution records of planktonic foraminifera and oxygen isotopes from two sediment cores, A7 and E017, in the middle Okinawa Trough reveal strong and rapid millennial-scale climate changes since similar to 18 to 17 thousand years before present (kyr B.P.). Sedimentation rate shows a sudden drop at similar to 11.2 cal. kyr B.P. due to a rapid rise of sea level after the Younger Dryas (YD) and consequently submergence of the large continental shelf on the East China Sea (ECS) and the retreat of the estuary providing sediment to the basin. During the last deglaciation, the relative abundance of warm and cold species of planktonic foraminifera fluctuates strongly, consistent with the timing of sea surface temperature (SST) variations determined from Mg/Ca measurements of planktonic foraminifera from one of the two cores. These fluctuations are coeval with climate variation recorded in the Greenland ice cores and North Atlantic sediments, namely Heinrich event 1 (H1), Bolling-Allerod (B/A) and YD events. At about 9.4 kyr B.P., a sudden change in the relative abundance of shallow to deep planktonic species probably indicates a sudden strengthening of the Kuroshio Current in the Okinawa Trough, which was synchronous with a rapid sea-level rise at 9.5-9.2 kyr B.P. in the ECS, Yellow Sea (YS) and South China Sea (SCS). The abundance of planktonic foraminiferal species, together with Mg/Ca based SST, exhibits millennial-scale oscillations during the Holocene, with 7 cold events (at about 1.7, 2.3-4.6, 6.2, 7.3, 8.2, 9.6, 10.6 cal. kyr BP) superimposed on a Holocene warming trend. This Holocene trend, together with centennial-scale SST variations superimposed on the last deglacial trend, suggests that both high and low latitude influences affected the climatology of the Okinawa Trough. (c) 2006 Elsevier B.V. All rights reserved.

A preliminary study on fingerprinting approach in marine sediment dynamics with the rare earth elements

Locating the quantitized natural sediment fingerprints is an important work for marine sediment dynamics study. The total of 146 sediment samples were collected from the Shelf of the East China Sea and five rivers, including Huanghe (Yellow), Changjiang (Yangtze), Qiantang, Ou and Min River. The sediment grain size and the contents of rare earth elements (REEs) were measured with laser particle size analyzer and ICP-MS technology. The results show that absolute REE content (Sigma REE) and the concentration ratio of light REEs to heavy REEs (L/HREE) are different in the sediments among those rivers. There are higher REE contents in being less than 2 m and 2-31 mu m fractions in the Changjiang Estuary surface sediments. The REE contents of bulk sediment are dominated by the corresponding values of those leading size-fractions. Sigma REE of sediment is higher close to the estuaries and declines seaward on the inner shelf of the East China Sea (ECS). The L/HREE ratio has a tendency of increase southward from 28 degrees N. Hydrodynamic conditions plays a predominate role on spacial distributions of the surficial sediment's REE parameters. In some situations, the currents tend to remove the coarser light grains from initial populations, as well as the deposit of the finer heavy mineral grains. In other situations, the currents will change the ratio of sediment constituents, such as ratio between silts and clays in the sediments. As a result, the various values of Sigma REE or L/HREE ratio in different bulk sediments are more affected by the change of size-fractions than source location. Under the long-term stable hydrodynamic environment, i.e., the East China Sea Shelf, new sediment transport model based on the size and density gradation concept may help to understand the spatial distribution patterns of REE parameters.

Warming trend in northern East China Sea in recent four decades

Global warming has become a notable trend especially since an abrupt climate change in 1976. Response of the East China Sea (ECS) to the global warming trend, however, is not well understood because of sparse long-term observation. In this paper, hydrographic observation data of 1957-1996 are collected and reviewed to study climatological variability in northern ECS. Significant warming trends are found in both summer and winter. In summer, the average SST is about 0.46A degrees C higher during the period of 1977-1996 than that of 1957-1976, and the Taiwan Warm Current Water (TWCW) was strengthened. In winter, despite of the cooling effect in the coastal areas adjacent to the Changjiang (Yangtze) River Estuary (CRE), the average SST increase was about 0.53A degrees C during the same period. The causes of this SST warming up in summer are different from in winter. The warming trend and intensification of the TWCW in summer were primarily influenced by the strengthening of the Kuroshio transport, while the warming in winter was mainly induced by the variability of the climate system.

THE EFFECTS OF MONSOONS AND CONNECTIVITY OF SOUTH CHINA SEA ON THE SEASONAL VARIATIONS OF WATER EXCHANGE IN THE LUZON STRAIT

Seasonal variations of water exchange in the Luzon Strait are studied numerically using the improved Princeton Ocean Model (POM) with a consideration of the effects of connectivity of South China Sea (SCS) and monsoons. The numerical simulations are carried out with the strategy of variable grids, coarse grids for the Pacific basin and fine grids for the SCS. It. is shown that the Mindoro Strait plays an important role in adjusting the water balance between the Pacific and the SCS. The SCS monsoon in summer seasons hinders the entrance of the Pacific water into the SCS through the Luzon Strait while the SCS monsoon in winter seasons promotes the entrance of Pacific water into the SCS through the Luzon Strait. However, the SCS monsoon does not affect the annual mean Luzon Strait transport, as is mainly determined by the Pacific basin wind.

胶州湾及其邻近海域的浮游植物－种类组成与数量变化

研究胶州湾浮游植物的物种组成与时空分布的特点，对于了解该湾生态系统的现状与历史变化趋势以及生态系统对自然条件变化和人类干扰的响应具有重要意义。 本文根据2004年每月一次采集的浮游植物样品，分析了胶州湾浮游植物的物种组成和优势种的时空分布情况。调查发现浮游植物共142种，分属于6门53属，其中硅藻门40属113种，占总物种数的79.6%；甲藻门10属24种，占总物种数的16.9%；其它为金藻门1属2种，裸藻1属1种，绿藻1属2种。浮游植物丰度周年波动范围为11.12－14602.39×104cells/m3，全年平均为1857.55×104cells/m3。全年丰度最高的藻为环纹劳德藻(Lauderia annulata)，出现在2月份，而全年的丰度最高值也出现在2月份。在胶州湾中，硅藻所占比例最大，平均为97.44%，最高为99.95%，最低为82.55%。浮游植物的丰度的周年变化：有两个高峰，分别出现在2月份和10月份，是典型的温带海域双高峰的分布形式。 胶州湾浮游植物的优势种分析，采用Kikvidze等（2002）提出的确定优势种数量的计算方法，再依据各物种的优势度排序最终确定优势种。其中在多样性最低的6月和10月，优势种数目均为1种，分别为丹麦细柱藻（Leptocylindrus danicus）和中肋骨条藻（Skeletonema costatum）。而在多样性指数较低的1月、2月，优势种数目分别为2和3；而在物种多样性比较高的5月、7月、11月，由于分布相对比较分散，所以优势种数量较多。这说明这个方法可以较好地完成对胶州湾浮游植物群落分析时确定优势种的目标。优势种出现频率较多的种类为中肋骨条藻（1、3、4、5、8、10、11、12月）、洛氏角毛藻(Chaetoceros lorenzianus)（7、8、9、11、12月）、尖刺拟菱形藻(Pseudonitzschia pungens)（2、3、5、7月）、加拉星杆藻(Asteronella kariana)（1、2、3、5月）、密联角毛藻(Chaetoceros densus)（5、11、12月）、扭鞘藻(Streptothece thamesis)（7、8、9月）、夜光藻(Noctiluca scintillancs)（4、5、7月）、奇异菱形藻(Nitzschia paradoxa)（5、11、12月）,对这些种的时空分布进行了分析。 对2004年胶州湾的浮游植物数据进行分层聚类分析后，发现可以将胶州湾划分为三个海区：湾南与湾外海区、湾中西部海区、湾东海区。