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.     

Coloured dissolved organic matter (CDOM) in Southern North Sea waters: Optical characterization and possible origin

The variability and origin of the Coloured Dissolved Organic Matter (CDOM) were studied in the Belgian coastal and adjacent areas including offshore waters and the Scheldt estuary, through the parameters: absorption at 375 nm, a_CDOM(375), and the slope of the absorption curve, S. a_CDOM(375) varied between 0.20 and 1.31 m⁻¹ and between 0.97 and 4.30 m⁻¹ in the marine area and Scheldt estuary, respectively. S fluctuated between 0.0101 and 0.0203 nm⁻¹ in the marine area and between 0.0167 and 0.0191 nm⁻¹ in the Scheldt estuary. The comparative analysis of a_CDOM(375) and S variations evidenced different origins of CDOM in the BCZ. The Scheldt estuarine waters showed decreasing a_CDOM(375) values with increasing salinity but constant S value of ∼0.018 nm⁻¹ suggesting a dominant terrestrial origin of CDOM. On the contrary, samples collected in the marine domain showed a narrow range of a_CDOM(375) but highly variable S suggesting the additional presence of autochthonous sources of CDOM. This source was evidenced based on the sorting of the marine offshore data according to the stage of the phytoplankton bloom when they were collected. A clear distinction was made between CDOM released during the growth stage characterized by high S (∼0.017 nm⁻¹) and low a_CDOM(375) and the decay phase characterized by low S (∼0.013 nm⁻¹) and high a_CDOM(375). This observation was supported by CDOM measurements performed on pure phytoplankton cultures which showed increased CDOM release along the wax and wane of the bloom but decreasing S. We concluded that the high variability of the CDOM signature in offshore waters is explained by the local biological production and processing of CDOM.     

Structure and photosynthetic properties of phytoplankton assemblages in a highly dynamic system, the Northern Adriatic Sea

The photosynthetic properties of phytoplankton populations as related to physical–chemical variations on small temporal and spatial scales and to phytoplankton size structure and pigment spectra were investigated in the Northern Adriatic Sea off the Po River delta in late winter 1997. Large diatoms (fucoxanthin) dominated the phytoplankton in the coastal area whereas small phytoflagellates (mainly 19′-hexanoyloxyfucoxanthin, chlorophyll b, 19′-butanoyloxyfucoxanthin) occurred outside the front. The front was defined by the steep gradient in density in the surface layer separating low-salinity coastal waters from the offshore waters.Physical features of the area strongly influenced phytoplankton biomass distributions, composition and size structure. After high volumes of Po River discharge several gyres and meanders occurred in the area off the river delta in February. Decreasing river discharge and the subsequent disappearance of the gyres and the spreading dilution of the river plume was observed in March. The dynamic circulation of February resulted in high photosynthetic capacity of the abundant phytoplankton population (>3.40 mg m⁻³). In March, the slow circulation and an upper low-salinity water layer, segregated from the deeper layers, resulted in lack of renewal of this water mass. The huge phytoplankton biomass, up to 15.77 mg chl a m⁻³, became nutrient depleted and showed low photosynthetic capacity. In February, an exceptionally high P_max^B, 20.11 mg C (mg chl a)⁻¹ h⁻¹ was recorded in the Po River plume area and average P_max^B was three-fold in February as compared to the March recordings, 10.50 mg C (mg chl a)⁻¹ h⁻¹ and 3.22 mg C (mg chl a)⁻¹ h⁻¹, respectively.The extreme variability and values of phytoplankton biomass in the innermost plume area was not always reflected in primary production. Modeling of circulation patterns and water mass resilience in the area will help to predict phytoplankton response and biomass distributions. In the frontal area, despite a considerable variability in environmental conditions, our findings have shown that the phytoplankton assemblages will compensate for nutrient depression and hydrographic constraints, by means of size and taxonomic composition and, as a result, the variability in the photosynthetic capacity was much less pronounced than that observed for other parameters.     

A tidal front in winter influenced by river discharge

Water quality of Osaka Bay is greatly influenced by freshwater discharge from rivers, to the effect of salinity playing a major role in forming the stratification. The tidal front is expected to appear in such an area even in winter considering the theory of the formation of a tidal front. From the field observation, we recognized a tidal front in winter for the first time in Osaka Bay. The critical value of a parameter log(H/U ³) for generation of a tidal front is obtained as a function of river discharge and cooling effect through sea surface. Differences of nutrients (NH₄–N, PO₄–P) concentration across the front are not clear, probably because they are utilized by phytoplankton easily. But in (NO₂–N)+(NO₃–N), DIN, PP and T–P, there is a discontinuity structure across the front, even if the absolute value of concentration difference is small.     

The proportions and variations of the light absorption coefficients of major ocean color components in the East China Sea

The East China Sea (ECS),one of the largest continental seas,has dynamic hydrology and complex optical characteristics that make ocean color remote-sensing retrieval difficult.The distributions and proportions of the light absorption coefficients of major ocean color components based on two large-scale investigations in the ECS are presented,showing these features in typical summer and winter seasons.The absorption coefficient a CDOM,a NAP and a phy of colored dissolved organic matter,non-algal particle,and pigment of phytoplankton show a decreasing trend from the coast to the outer shelf.According to the a CDOM distribution at 440 nm,the Changjiang River plume shows an abnormal southeastward transport.An extremely high a NAP value patch at 440 nm is present in the middle coast.The chlorophyll-a-specific phytoplankton pigment absorption (a phy) is much higher in winter than in summer,which may cause serious underestimated results when applying the averaged a phy into remote-sensing algorithms for chlorophyll concentration retrieval.The importance of phytoplankton size was evident in outer shelf waters.The absorption of a CDOM (440) is a dominant component accounting for over half of the total seawater absorption in summer.The a NAP (440) accounts for 64% of the absorption of the ECS coastal area in winter.     

Microphytobenthos vertical migratory photoresponse as characterised by light-response curves of surface biomass

The migratory response of intertidal microphytobenthos to changes in irradiance was studied on undisturbed estuarine sediments. Two non-destructive optical techniques were used to trace variations in vivo of surface biomass: PAM fluorometry, for measuring the minimum fluorescence level (F_o); and spectral reflectance analysis, for quantifying the normalized difference vegetation index (NDVI). Following the formation of a dense biofilm at the surface, replicated sediment samples were simultaneously exposed to six different irradiance levels, ranging from 50 to 1500 μmol m⁻² s⁻¹, during a period of 120 min. The migratory photoresponse of the biofilms was characterised by constructing biomass vs. light curves (BLC), relating the accumulation of microalgal biomass after that period (estimated by F_o or NDVI) to the irradiance level incident on the surface. BLCs allow characterising the main features of the migratory photoresponse of intact biofilms. Typical BLC showed a clear biphasic pattern, with an increase in microalgal accumulation under irradiances below 100 μmol m⁻² s⁻¹, maximum values under 100–250 μmol m⁻² s⁻¹, and a gradual decrease of surface biomass under higher irradiances, indicating a strong photophobic downward migratory response. Similar BLC patterns were obtained when measuring F_o or NDVI. The construction of BLCs for biofilms from intertidal sites with distinctive sediment characteristics and diatom taxonomic composition allowed to detected significant differences in the migratory photoresponse. Biofilms from a muddy sediment exhibited considerably larger amplitude in the migratory photoresponse than the biofilms from a sandy mud site, especially under high irradiances. The photophobic migratory response to high light was found to vary among diatom species, particularly in the case of the biofilms from the muddy sediments.     

A dense bottom water plume in the western Barents Sea: downstream modification and interannual variability

The generation and downstream modification of a cold dense Arctic shelf water plume were studied with moored current meters, thermistor chains and conductivity/temperature sensors deployed from August 1993 to September 1994 south of the Storfjord in the Svalbard Archipelago. These observations are compared to similar time series from 1991/92. In 1993/94, bottom water with temperatures close to the freezing point drained continuously from Storfjord between March and September with a mean speed of 0.14 m s⁻¹. About 1.5 months after the plume front had left the Storfjord, it reached the shelf break, 150 km away. The plume had increased its width from 15 km to about 35 km, but its thickness of 50 m remained almost constant and it left the shelf edge at a similar speed. The increased volume transport and the change of temperature/salinity properties indicate an entrainment of 110% of ambient Atlantic water into the plume on its way from the production area to the shelf edge.The maximum salinity of the cold plume was 0.2 lower in 1993/94 than in 1991/92, whilst the temperature/salinity-range of the surrounding Atlantic water remained unchanged. Probably as a dynamic consequence, the speed of the plume was considerably lower in 1993/94. The lower salinity of the plume in 1993/94 is a result of both the 30% less ice formation in Storfjord, caused by lower heat flux and less open water, and a lower surface salinity at the beginning of ice formation. During 1993/94, the Storfjord plume was too light to sink below 700 m.     

The spatial distribution of surface <Emphasis Type="Italic">f</Emphasis>CO<Subscript>2</Subscript> in the Southwestern East Sea/Japan sea during summer 2005

Fugacity of CO₂ (fCO₂), temperature, salinity, nutrients, and chlorophyll-a were measured in the surface waters of southwestern East Sea/Japan Sea in July 2005. Surface waters were divided into three waters based on hydrographic characteristics: the water with moderate sea surface temperature (SST) and high sea surface salinity (SSS) located east of the front (East water); the water with high SST and moderate SSS located west of the front (West water); and the water with low SST and SSS located in the middle part of the study area (Middle water). High fCO₂ larger than 420 μatm were found in the West water. In the Middle water, CO₂ was undersaturated with respect to the atmosphere, with values between 246 and 380 μatm. Moderate fCO₂ values ranging from 370 to 420 μatm were observed in the East water. For the East and West waters, estimates of temperature dependency of fCO₂ (12.6 and 15.1 μatm °C⁻¹, respectively) were rather similar to a theoretical value, indicating that SST is likely to be a major factor controlling the surface fCO₂ distribution in these two regions. In the Middle water, however, the estimated temperature dependence was somewhat lower than the theoretical value, and relatively high concentrations of surface chlorophyll-a coincided with the low surface fCO₂, implying that biological uptake may considerably affect the fCO₂ distribution. The net sea-to-air CO₂ flux of the study area was estimated to be 0.30±4.81 mmol m⁻² day⁻¹ in summer, 2005.     

A three-dimensional hydrodynamic model of estuarine circulation with an application to Southampton Water, UK

A three-dimensional hydrodynamic model has been developed to simulate water mass circulation in estuarine systems. This model is based on the primitive equation in Cartesian coordinates with a terrain-following structure, coupled with a Mellor–Yamada 2.5 turbulence scheme. A fractional-step method is applied and the subset of equations is solved with finite volume and finite element methods. A dry–wet process simulates the presence of the tidal flat at low water. River inputs are introduced using a point-source method. The model was applied to a partially mixed, macrotidal, temperate estuary: Southampton Water, UK. The model is validated by comparisons with sea surface elevation, ADCP measurements and salinity data collected in 2001. The mean spring range 2(M₂ + S₂) and the mean neap range 2(M₂ − S₂) are modelled with an error relative to observation of 12 and 16%, respectively. The unique tidal regime of the system with the presence of the ‘young flood stand’ corresponding to the slackening conditions occurring at mid flood and ‘double high water’ corresponding to an extension of the slackening conditions at high tide is accurately reproduced in the model. The dynamics of the modelled mean surface and bottom velocity closely match the ADCP measurements during neap tides (rms of the difference is 0.09 and 0.01 m s⁻¹ at the bottom and at the surface, respectively), whereas at spring the difference is greater (rms of the difference is 0.25 and 0.20 m s⁻¹ at bottom and surface, respectively). The spatial and temporal variation of the degree of stratification as indicated by salinity distributions compares well with observations.     

考洲洋牡蛎养殖海域海-气界面CO2交换通量的时空变化

根据2018年7月、11月和2019年1月、4月对广东考洲洋牡蛎养殖海域进行4个季节调查获得的p H、溶解无机碳(DIC)、水温、盐度、溶解氧(DO)及叶绿素a(Chla)等数据,估算该区域表层海水溶解无机碳体系各分量的浓度、初级生产力(PP)、表层海水CO₂分压[p(CO₂)]和海-气界面CO₂交换通量(FCO₂),分析牡蛎养殖活动对养殖区碳循环的影响。结果表明:牡蛎养殖区表层海水中Chl a、DIC、HCO₃^–和PP显著低于非养殖区;养殖淡季表层海水中pH、DO、DIC、HCO₃^–、和CO₃^2–显著大于养殖旺季,养殖旺季的p(CO₂)和FCO₂显著大于养殖淡季。牡蛎养殖区表层海水夏季、秋季、冬季和春季的海-气界面CO₂交换通量FCO₂平均值分别是(42.04±9.56)、(276...     

Effect of changes in water salinity on ammonium, calcium, dissolved inorganic carbon and influence on water/sediment dynamics

The effect of a sudden increase in salinity from 10 to 37 in porewater concentration and the benthic fluxes of ammonium, calcium and dissolved inorganic carbon were studied in sediments of a small coastal lagoon, the Albufera d'Es Grau (Minorca Island, Spain). The temporal effects of the changes in salinity were examined over 17 days using a single diffusion-reaction model and a mass-balance approach. After the salinity change, NH₄⁺-flux to the water and Ca-flux toward sediments increased (NH₄⁺-flux: 5000–3000 μmol m⁻² d⁻¹ in seawater and 600/250 μmol m⁻² d⁻¹ in brackish water; Ca-flux: −40/−76 meq m⁻² d⁻¹ at S=37 and −13/−10 meq m⁻² d⁻¹ at S=10); however, later NH₄⁺-flux decreased in seawater, reaching values lower than in brackish water. In contrast, Ca-flux presented similar values in both conditions. The fluxes of dissolved inorganic carbon, which were constant at S=10 (55/45 mmol m⁻² d⁻¹), increased during the experiment at S=37 (from 30 mmol m⁻² d⁻¹ immediately after salinity increase to 60 mmol m⁻² d⁻¹ after 17 days).In brackish conditions, NH₄⁺ and Ca²⁺ fluxes were consistent with a single diffusion-reaction model that assumes a zero-order reaction for NH₄⁺ production and a first-order reaction for Ca²⁺ production. In seawater, this model explained the Ca-flux observed, but did not account for the high initial flux of NH₄⁺.The mass balance for 17 days indicated a higher retention of NH₄⁺ in porewater in the littoral station in seawater conditions (9.5 mmol m⁻² at S=37 and 1.6 mmol m⁻² at S=10) and a significant reduction in the water consumption at both sites (5 mmol m⁻² at S=37; 35/23 mmol m⁻² at S=10). In contrast, accumulation of dissolved inorganic carbon in porewater was lower in seawater incubations (−10/−1 meq m⁻² at S=37; 50/90 meq m⁻² at S=10) and was linked to a higher efflux of CO₂ to the atmosphere, because of calcium carbonate precipitation in water (675/500 meq m⁻²). These results indicate that increased salinity in shallow coastal waters could play a major role in the global carbon cycle.     

Spatial and Temporal Variation of Surface xCO<Subscript>2</Subscript> Providing Net Biological Productivities in the Western North Pacific in June

More than 14,000 measurements of surface water xCO₂ were obtained during two cruises, 3 weeks apart in June 2000, along 155°E between 34 and 44°N in the western North Pacific Ocean. Based on the distributions of salinity and sea surface temperature (SST), the region has been divided into 6 subregions; Oyashio, Oyashio front, Transition, Kuroshio front, and Kuroshio extension I and II zones, from north to south. The surface waters were always undersaturated with respect to atmospheric CO₂. The Oyashio water was the least undersaturated: its xCO₂ decreased slightly by 7 ppm, while SST increased by 2°C. The xCO₂ normalized to a constant temperature decreased considerably. In the two frontal zones, a large drawdown of 30–40 ppm was observed after 18–19 days. In the Kuroshio extension zones, the xCO₂ increased, but the normalized xCO₂ decreased considerably. The Transition zone water may be somewhat affected by mixing with the subsurface water, as indicated by the smallest SST rise, an undecreased PO₄ concentration, and a colder and less stable surface layer than the Oyashio front water. As the uncertainty derived from the air-sea CO₂ flux was not large, the xCO₂ data allowed us to calculate the net biological productivity. The productivities around 60 mmol C m⁻²d⁻¹ outside the Transition zone indicate that the northwestern North Pacific, especially the two frontal zones, can be regarded as one of the most productive oceans in the world.     

Measurement of a negatively buoyant plume in the coastal waters off freeport, Texas

Continuous discharge of a nominal 230 part per thousand brine solution was initiated in March 1980 at a rate of approx. 225,000 barrels/day (3.58 × 10 ⁷ l/day) from a submerged multiport diffuser in 70 ft (21.3 m) of water at a distance of 12.5 statute miles (20 km) off the Freeport, Texas coast. A measurement system is described which was designed and used to measure the excess salinity and areal extent of the negatively buoyant brine plume. This system consists of a towing sled in which an in situ conductivity, temperature and depth probe is mounted. The towing sled is towed by Texas A & M University's research vessel, R.V. Excellence, on a predetermined search course through the expected plume area. The probe continuously measures the salinity at distance of 10 in. (25.4 cm) above the sea floor.The measured salinity data are used to construct isohalines of the bottom area, or plume contours, which indicate the areal coverage of the plume and the magnitude of the excess salinity concentration. Vertical salinity profiles were also measured in the plume area to evaluate the vertical extent of the plume.Plume contours and vertical profiles constructed from the data collected on 22, 30 March and 10 April, 1980 are discussed. The largest excess salinity contour was 5 parts per thousand above ambient and the area inside this contour was 6 acres (0.02 km². The highest vertical extent of the plume was 25 ft (4.6 m). These measurements indicated the bottom mounted diffuser system was successfully diluting the highly concentrated brine solution and natural processes of advection and diffusion were dispersing the plume satisfactorily.     

Measurements of the water-following capability of holey-sock and TRISTAR drifters

Since 1985, a number of measurements have been made in deep water to determine the water-following characteristics of mixed layer drifters with both holey-sock and TRISTAR drogues at 15 m depth. The measurements were done by attaching two neutrally buoyant vector measuring current meters (VMCMs) to the top and the bottom of the drogues and deploying the drifters in different wind and upper ocean shear conditions for periods of 2–4 h. The average velocity of the VMCM records was taken to be a quantitative measure of the slip of the drogue through the water, observed to be 0.5-3.5 cm s⁻¹. The most important hydrodynamic design parameter which influenced the slip of the drogue was the ratio of the drag area of the drogue to the sum of the drag areas of the tether and surface floats: the drag area ratio R. The most important environmental parameters which affected the slip were the wind and the measured velocity difference across the vertical extent of the drogue. A model of the vector slip as a function of R, vector wind and velocity difference across the drogue was developed and a least squares fit accounts for 85% of the variance of the slip measurements. These measurements indicated that to reduce the wind produced slip below 1 cm s⁻¹ in 10 m s⁻¹ wind speed, R > 40. Conversely, if the daily average wind is known to 5 m s⁻¹ accuracy, the displacement of the R = 40 drifter can be corrected to an accuracy of 0.5 km day⁻¹.     

Seasonal and interannual variability of the air–sea CO2 flux in the Atlantic sector of the Barents Sea

The seasonal and interannual variability of the air–sea CO₂ flux (F) in the Atlantic sector of the Barents Sea have been investigated. Data for seawater fugacity of CO₂ (fCO₂^sw) acquired during five cruises in the region were used to identify and validate an empirical procedure to compute fCO₂^sw from phosphate (PO₄), seawater temperature (T), and salinity (S). This procedure was then applied to time series data of T, S, and PO₄ collected in the Barents Sea Opening during the period 1990–1999, and the resulting fCO₂^sw estimates were combined with data for the atmospheric mole fraction of CO₂, sea level pressure, and wind speed to evaluate F.The results show that the Atlantic sector of the Barents Sea is an annual sink of atmospheric CO₂. The monthly mean uptake increases nearly monotonically from 0.101 mol C m^− 2 in midwinter to 0.656 mol C m^− 2 in midfall before it gradually decreases to the winter value. Interannual variability in the monthly mean flux was evaluated for the winter, summer, and fall seasons and was found to be ± 0.071 mol C m^− 2 month^− 1. The variability is controlled mainly through combined variation of fCO₂^sw and wind speed. The annual mean uptake of atmospheric CO₂ in the region was estimated to 4.27 ± 0.68 mol C m^− 2.     

长江河口盐度锋

根据1988－1991年河口锋面现场调查、上海市海岸带调查及历次标准断面调查资料对长江盐度场及盐度锋进行了分析，提出了由口门至外海纵向上存在着三级锋面现象：内侧锋面即长江河口锋为长江河口水与长江冲淡水的界面；羽状锋是长江口羽状流水与口外混合水的界面，它是长江口最主要的盐度锋面，也是长江口一个重要的生物地球化学带，对河口沉积过程及水下三角洲发育具有重要的影响。外侧锋面即海洋锋，是长江冲淡水的最外边缘。     

The coriolis effect against frontogenesis in steady buoyancy-driven circulation

The Coriolis effect on frontogenesis in the transitional region between the inner bay and the outer ocean is studied by running several three-dimensional numerical experiments. The aim is to clarify what external parameters, including the transverse scale of the basin, control the phenomena. The characteristics of the front in each case are described by defining three diagnostic quantities, namely, the sharpness of the front, the intrusion of the front, and the buoyancy difference between the minimum buoyancy region and the surrounding part, as the existence of the minimum buoyancy region is closely related to frontogenesis. The three quantities are shown to depend on two nondimensional numbers,R _of (=f ⁻¹ L ^−2/3 F _b ^1/3 : defined as flux Rossby number) andR _ef (=ν _v ⁻¹ L ^−2/3 F _b ^1-3 H ²: defined as flux Reynolds number).     

Spectrophotometric pH measurement in estuaries using thymol blue and m-cresol purple

The conditional acid dissociation constants (pK_a′) of two sulfonephthalein dyes, thymol blue (TB) and m-cresol purple (mCP), were assessed throughout the estuarine salinity range (0<S<40) using a tris/tris–HCl buffer and spectrophotometric measurement. The salinity dependence of the pK_a′ of both dyes was fitted to the equations (25 °C, total proton pH scale, mol kg soln⁻¹):

The estimated accuracy of pH measurements using these calculated pK_a′ values is considered to be comparable to that possible with careful use of a glass electrode (±0.01 pH unit) but spectrophotometric measurements in an estuary have the significant advantage that it is not necessary to calibrate an electrode at different salinities. pH was measured in an estuary over a tidal cycle with a precision of ±0.0005 pH unit at high (S>30) salinity, and ±0.002 pH unit at low (S<5) salinity. The pH increased rapidly in the lower salinity ranges (0<S<15) but less rapidly at higher salinities.     

Hydrothermal plumes in the eastern Manus Basin, Bismarck Sea: CH4, Mn, Al and pH anomalies

We present evidence for strong hydrothermal activity in the eastern Manus Basin (depth: 1700–2100 m), the existence of large scale triple-layered buoyant plumes at depths of 1100 m (“shallow plume”), 1700 m (“deep plume”), and 1400 m (“middle plume” with less extent than the other two plumes) that were revealed from water column anomalies of CH₄, Mn, Al and pH observed in November to December 1990. Judging from the horizontal distribution of these parameters, the deep plume seems to originate from two distinct hydrothermal sites (eastern and western sites) in the research area, the eastern site being visually ascertained with deep-tow observations at the same time. The CH₄/Mn ratio (mol mol⁻¹) of the deep plume (0.02–0.05) is the lowest yet observed in hydrothermal plumes. The order of magnitude difference of CH₄/Mn ratios between the shallow plume and the deep plume suggests that different kinds of fluid-rock interaction occurred to make the hydrothermal end members for the deep and shallow plumes. The shallow plume, which had an areal extent of more than 50 km, may be an episodic “megaplume”, because it was not recognized in the previous CH₄ profiles in 1986, and because it has a similar CH₄/Mn ratio as the megaplume observed in the North Fiji Basin. We found that the eastern deep plume is characterized by enormously high aluminium concentrations (0.6– 1.5 μmol kg⁻¹), pH anomalies (0.1) and high Al/Mn ratios (10–17). The endmember fluid for the eastern deep plume may have an unusually low pH value to dissolve this much aluminum during fluid-rock interaction, or this plume may originate from an eruption-influenced fluid.     

Sediment–water interactions of natural oestrogens under estuarine conditions

The natural human female hormones oestrone and 17β-oestradiol have been implicated in the disruption of endocrine systems in some wildlife adjacent to sewage effluents. The sorption behaviour of these two compounds under estuarine conditions was studied by spiking either 2.55 μg of oestrone or 2.65 μg of 17β-oestradiol in kinetic experiments. In equilibrium experiments, 3 ng of oestrone or 3.2 ng of 17β-oestradiol was added in each of the centrifuge tubes. Sorption onto sediment particles was relatively slow, with sorption equilibrium being reached in about 70 and 170 h for oestrone and 17β-oestradiol, respectively. The effects of a variety of environmental parameters on sorption were studied including salinity, sediment concentration (SC), the presence of a third phase, particle size and, also, surfactant concentrations. Results show that although salinity did not induce any statistically significant effect on the sorption of 17β-oestradiol, it did statistically enhance the sorption of oestrone, and a salting constant of 0.3 l mol⁻¹ was derived. The partition coefficient for both compounds decreased with increasing sediment concentration, a phenomenon that has been widely reported and attributed to the presence of colloids (which could enhance dissolved concentrations). In this paper, the true partition coefficients for sediment particles (K_p^true) and colloidal particles (K_c^true) have been calculated, and a K_p^true value of 141 and 102 ml g⁻¹ was obtained for oestrone and 17β-oestradiol, respectively. In addition, K_c^true values for oestrone (222×10² ml g⁻¹) and 17β-oestradiol (135×10² ml g⁻¹) were two orders of magnitude higher than their respective K_p^true values, suggesting that the colloidal particles are significantly stronger sorbents for natural oestrogens than sediment particles. Particles of different sizes were found to have different partition coefficients due to the strong relationships between partition coefficients for the two compounds and particulate organic carbon (POC) contents and specific surface areas (SSAs). The presence of a surfactant was shown to reduce the partition coefficients for the two compounds, although its concentrations being used were higher than those normally found in the natural environment.