Optical properties of low molecular weight and colloidal organic matter: Application of the ultrafiltration permeation model to DOM absorption and fluorescence

Cross-flow ultrafiltration (CFF) is often used to obtain separation and concentration of colloids from bulk natural water samples. Application of the ultrafiltration permeation model allows the quantitative determination of the low molecular weight material (LMW, < 1 kDa) and colloids in bulk dissolved organic matter (DOM) from measurements of time series permeate samples obtained from CFF. Detailed analysis of a Yukon River water sample shows that DOM absorption coefficient and fluorescence follow the permeation model and that the complex spectral optical properties of LMW DOM can be reconstructed from CFF data. A combination of measured and modeled data indicates that the LMW contribution to bulk DOM optical properties obtained from CFF can be grossly underestimated by the use of a low concentration factor (CF, the ratio of initial sample volume to retentate volume). Even at a relatively high CF of 19, optical properties of LMW DOM calculated from measurements of the retentate or integrated permeate would underestimate true values by 5–36%. In the Yukon River sample, LMW dissolved organic carbon represented 26% of the bulk concentration, but only 3–14% of the colored DOM was in the LMW fraction while 31–33% of bulk DOM florescence was due to LMW DOM. The contrasting optical properties of LMW and colloidal DOM support the concept that analysis of bulk DOM absorption and fluorescence properties reveals information about DOM molecular weight.     

Distribution of whitemouth croaker (Micropogonias furnieri, Desmarest 1823) larvae in the Río de la Plata estuarine front

Whitemouth croaker (Micropogonias furnieri) larvae obtained and hydrographic data collected in the Rio de la Plata estuary (35°S–56°W) between 1987 and 2000 were used to explore the early life stages spatial and temporal distribution patterns and their relation to oceanographic features. The spatial distribution, restricted to a band in the inner part of the estuary, coincided with the bottom salinity front and the maximum turbidity zone (MTZ, turbidity front). Larvae were present during the warmest months (October through May) within a range of 14–24.5 °C temperature and 0.9–33 salinity. A vertically stratified sampling performed in the region where the largest abundance was found (December 2005 and March 2006) was used to test the hypothesis that larvae retention occurs in the bottom salinity front.The vertically stratified sampling showed larvae throughout the water column with high predominance in the river–estuary transition zone. A positive correlation between abundance and the bottom salinity horizontal gradient was found. The size analysis showed that the largest individuals (>10 mm SL), probably undergoing the settlement process, inhabited near the bottom and that the smallest (<10 mm SL) were present in the whole water column. Length distribution along the front showed no trend.Results support the estuarine retention hypothesis of previous studies on whitemouth croaker gravid females, eggs distribution and outcomes from a numerical simulation model. Retention in the salinity front/MTZ would allow larvae to benefit from food accumulation in the region, the high turbidity level provide shelter against predators and retention in the estuary secure closeness to the main nursery ground.     

Horizontal distribution and population dynamics of the dominant mysid Hyperacanthomysis longirostris along a temperate macrotidal estuary (Chikugo River estuary, Japan)

The estuarine turbidity maximum (ETM) that develops in the lower salinity areas of macrotidal estuaries has been considered as an important nursery for many fish species. Mysids are one of the dominant organisms in the ETM, serving as a key food source for juvenile fish. To investigate the horizontal distribution and population dynamics of dominant mysids in relation to the fluctuation of physical conditions (temperature, salinity, turbidity, and freshwater discharge), we conducted monthly sampling (hauls of a ring net in the surface water) along the macrotidal Chikugo River estuary in Japan from May 2005 to December 2006. Hyperacanthomysis longirostris was the dominant mysid in the estuary, usually showing peaks of density and biomass in or close to the ETM (salinity 1–10). In addition, intra-specific differences (life-cycle stage, sex, and size) in horizontal distribution were found along the estuary. Larger males and females, particularly gravid females, were distributed upstream from the center of distribution where juveniles were overwhelmingly dominant. Juveniles increased in size toward the sea in marked contrast with males and females. The findings suggest a possible system of population maintenance within the estuary; gravid females release juveniles in the upper estuary, juveniles grow during downstream transport, young males and females mature during the upstream migration. Density and biomass were primarily controlled by seasonal changes of temperature, being high at intermediate temperatures (ca. 15–25 °C in late spring and fall) and being low at the extreme temperatures (ca. 10 °C in midwinter and 30 °C in midsummer). High density (up to 666 ind. m⁻³) and biomass (up to 168 mg dry weight m⁻³) of H. longirostris were considered to be comparable with those of copepods in the estuary.     

Biogeochemical transport in the Loxahatchee River estuary, Florida: The role of submarine groundwater discharge

The distributions of dissolved organic carbon (DOC), Ba, U, and a suite of naturally occurring radionuclides in the U/Th decay series (²²²Rn, ^{223,224,226,228}Ra) were studied during high- and low-discharge conditions in the Loxahatchee River estuary, Florida to examine the role of submarine groundwater discharge in estuarine transport. The fresh water endmember of this still relatively pristine estuary may reflect not only river-borne constituents, but also those advected during active groundwater/surface water (hyporheic) exchange. During both discharge conditions, Ba concentrations indicated slight non-conservative mixing. Such Ba excesses could be attributed either to submarine groundwater discharge or particle desorption processes. Estuarine dissolved organic carbon concentrations were highest at salinities closest to zero. Uranium distributions were lowest in the fresh water sites and mixed mostly conservatively with an increase in salinity. Suspended particulate matter (SPM) concentrations were generally lowest (< 5 mg L^− 1) close to zero salinity and increased several-fold ( 18 mg L^− 1; low discharge) toward the seaward endmember, which may be attributed to dynamic resuspension of bottom sediments within Jupiter Inlet.Surface water-column ²²²Rn activities were most elevated (> 28 dpm L^− 1) at the freshwater endmember of the estuary and appear to identify regions of the river most influenced by the discharge of fresh groundwater. Activities of four naturally occurring isotopes of Ra (^{223,224,226,228}Ra) in this estuary and select adjacent shallow groundwater wells yield mean estuarine water-mass transit times of less than 1 day; these values are in close agreement to those calculated by tidal prism and tidal frequency. Submarine groundwater discharge rates to the Loxahatchee River estuary were calculated using a tidal prism approach, an excess ²²⁶Ra mass balance, and an electromagnetic seepage meter. Average SGD rates ranged from 1.0 to 3.8 × 10⁵ m³ d^− 1 (20–74 L m^− 2 d^− 1), depending on river-discharge stage. Such calculated SGD estimates, which must include both a recirculated as well as fresh water component, are in close agreement with results obtained from a first-order watershed mass balance. Average submarine groundwater discharge rates yield NH₄⁺ and PO₄^− 3 flux estimates to the Loxahatchee River estuary that range from 62.7 to 1063.1 and 69.2 to 378.5 μmol m^− 2 d^− 1, respectively, depending on river stage. SGD-derived nutrient flux rates are compared to yearly computed riverine total N and total P load estimates.     

Natural organics as fluorescent tracers of river-sea mixing

The use of dissolved organic matter fluorescence as a tracer of river-sea mixing was examined in two South Carolina estuaries. Fluorescence declined linearly with seawater dilution in laboratory mixing studies, and also behaved conservatively in an estuary where a single river emptied into a bay. Fluorescence-salinity relationships were also studied in another estuary where a piedmont river (high suspended sediment, low fluorescence) and a coastal plains river (low sediment, high fluorescence) mixed with ocean water. The factor of 2 or greater difference in fluorescence between the two rivers allowed their relative contribution to the estuarine water mass to be distinguished. Petroleum hydrocarbons, measured in estuarine water at 0·7-1·8 μg l⁻¹ concentrations, contributed negligibly to water fluorescence.     

Optical properties of estuarine dissolved organic matter isolated using cross-flow ultrafiltration

Dissolved organic matter(DOM) from freshwater, mid-salinity, and seawater endmember samples in the Jiulong River Estuary, China were fractionated using cross-flow ultrafiltration with a 10-kDa membrane. The colloidal organic matter(COM; 10 kDa–0.22 μm) retentate, low molecular weight(LMW) DOM(10 kDa) permeate, and bulk samples were analyzed using absorption spectroscopy and three-dimensional fluorescence excitation-emission-matrix spectroscopy. The UV-visible spectra of COM were very similar to those obtained for permeate and bulk samples, decreasing monotonically with increasing wavelength. Most of the chromophoric DOM(CDOM, expressed as the absorption coefficient a355) occurred in the LMW fraction, while the percentage of CDOM in the colloidal fraction was substantially higher in the freshwater endmember(13.4% of the total) than in the seawater endmember(6.8%). The bulk CDOM showed a conservative mixing behavior in the estuary, while there was removal of the COM fraction and a concurrent addition of the permeate fraction in the mid-salinity sample, implying that part of the colloidal CDOM was transformed into LMW CDOM. Two humic-like components(C1: 250, 325/402 nm; and C2: 265, 360/458 nm) and one protein-like component(C3: 275/334 nm) were identified using parallel factor analysis. The contributions of the C1, C2, and C3 components of the COM fraction to the bulk sample were 2.5%–8.7%, 4.8%–12.6%, and 7.4%–14.7%, respectively, revealing that fluorescent DOM occurred mainly in the LMW fraction in the Jiulong River Estuary. The C1 and C2 components in the retentate and permeate samples showed conservative mixing behavior, but the intensity ratio of C2/C1 was higher in the retentate than in the permeate fractions for all salinity samples, showing that the humic component was more enriched in the COM than the fulvic component. The intensity ratio of C3/(C1+C2) was much higher in the retentate than in the permeate fraction for mid-salinity and seawater samples, revealing that the protein-like component was relatively more enriched in COM than the humic-like component. The contribution of the protein-like component(C3) to the total fluorescence in the retentate increased from 14% in the freshwater endmember to 72% for the seawater endmember samples, clearly indicating the variation of dominance by the humic-like component compared to the protein-like component during the estuarine mixing process of COM.     

The impact of groundwater discharges on mercury partitioning, speciation and bioavailability to mussels in a coastal zone

The Mussel Watch program conducted along the French coasts for the last 20 years indicates that the highest mercury concentrations in the soft tissue of the blue mussel (Mytilus edulis) occur in animals from the eastern part of Seine Bay on the south coast of the English Channel, the “Pays de Caux”. This region is characterized by the presence of intertidal and submarine groundwater discharges, and no particular mercury effluent has been reported in its vicinity. Two groundwater emergence systems in the karstic coastal zone of the Pays de Caux (Etretat and Yport with slow and fast water percolation pathways respectively) were seasonally sampled to study mercury distribution, partitioning and speciation in water. Samples were also collected in the freshwater–seawater mixing zones in order to compare mercury concentrations and speciation between these “subterranean” or “groundwater” estuaries and the adjacent macrotidal Seine estuary, characterized by a high turbidity zone (HTZ). The mercury concentrations in the soft tissue of mussels from the same areas were monitored at the same time.The means of the “dissolved” (< 0.45 μm) mercury concentrations (HgT_D) in the groundwater springs were 0.99 ± 0.15 ng l^− 1 (n = 18) and 0.44 ± 0.17 ng l^− 1 (n = 17) at Etretat and Yport respectively. High HgT_D concentrations were associated with strong runoff over short water pathways during storm periods, while low concentrations were associated with long groundwater pathways. Mean particulate mercury concentrations were 0.22 ± 0.05 ng mg^− 1 (n = 16) and 0.16 ± 0.10 ng mg^− 1 (n = 17) at Etretat and Yport respectively, and decreased with increasing particle concentration probably as a result of dilution by particles from soil erosion. Groundwater mercury speciation was characterized by high reactive-to-total mercury ratios in the dissolved phase (HgR_D/HgT_D: 44–95%), and very low total monomethylmercury concentrations (MMHg < 8 pg l^− 1). The HgT_D distributions in the Yport and Etretat mixing zones were similar (overall mean concentration of 0.73 ± 0.21 ng l^− 1, n = 43), but higher than those measured in the adjacent industrialized Seine estuary (mean: 0.31 ± 0.11 ng l^− 1, n = 67). In the coastal waters along the Pays de Caux dissolved monomethylmercury (MMHg_D) concentrations varied from 9.5 to 13.5 pg l^− 1 (2 to 8% of the HgT_D). Comparable levels were measured in the Seine estuary (range: 12.2– 21.1 pg l⁻¹; 6–12% of the HgT_D). These groundwater karstic estuaries seem to be mostly characterized by the higher HgT_D and HgR_D concentrations than in the adjacent HTZ Seine estuary. While the HTZ of the Seine estuary acts as a dissolved mercury removal system, the low turbid mixing zone of the Pays de Caux receives the dissolved mercury inputs from the groundwater seepage with an apparent Hg transfer from the particulate phase to the “dissolved” phase (< 0.45 μm). In parallel, the soft tissue of mussels collected near the groundwater discharges, at Etretat and Yport, exhibited significantly higher values than those found in the mussel from the mouth of the Seine estuary. We observe that this difference mimics the differences found in the mercury distribution in the water, and argue that the dissolved phase of the groundwater estuaries and coastal particles are significant sources of bioavailable mercury for mussels.     

Behaviour of proteinaceous substances in the estuary of the Tama River

Behaviour of dissolved and particulate proteinaceous substances in the estuary of the Tama River was investigated through field observations and laboratory experiments. Concentrations of dissolved proteinaceous substances in estuarine water were determined at eight stations between the mouth of the Tama River (TA-15) and a point 16km upstream (TA-8), using the colorimetric method of Lowryet al. (1951) that employs Folin phenol reagent. The results were expressed in terms of Folin phenol active substances (FPAS). It was found that FPAS decreased with increasing salinity and that the proportion of high molecular weight FPAS (molecular weight greater than 100,000) decreased rapidly in the estuary.The shapes, sizes and numbers of amorphous particulate substances stained by Amido Black 10B, called Amido Black active substances (ABAS), were determined under a microscope. The numbers of ABAS retained on Millipore HA filters (mean diameter: 10–80µm) amounted to 450ml^–1 in the estuarine water about 6km from the mouth of the estuary (Station TA-12M). Some of these aggregates are considered to be producedin situ by flocculation of high molecular weight FPAS during estuarine mixing. ABAS were also produced in experiments by mixing filtered river water with sea water.     

Behaviour of colloidal trace metals (Cu, Pb and Cd) in estuarine waters: An approach using frontal ultrafiltration (UF) and stripping chronopotentiometric methods (SCP)

The frontal cascade ultrafiltration (UF) technique in conjunction with stripping chronopotentiometry (SCP) has been evaluated for determining the colloidal distribution of Cu, Pb and Cd in estuarine waters. Metallic concentrations in seven size fractions (0.45 μm–0.22 μm; 0.22 μm–300 kDa; 300–50 kDa; 50–30 kDa; 30–10 kDa; 10–5 kDa; <5 kDa) were determined with the aim to investigate their changes along the salinity gradient of the Penzé system (NW France). These data, completed by analysis of the total dissolved metals at 10 stations over the whole freshwater–seawater mixing zone, provided some insights in the removal and addition processes that affect Cu, Pb and Cd in estuaries.     

Dissolved uranium, vanadium and molybdenum behaviours during contrasting freshwater discharges in the Gironde Estuary (SW France)

Understanding trace metal behaviour in estuarine environments requires sampling strategies and analytical methods adapted to strong physical and geochemical gradients. In this study, we present a specific sampling strategy covering a wide range of hydrological conditions during nine cruises in 2003–2007 to characterise the behaviour of three dissolved metals (uranium, vanadium and molybdenum) in surface and bottom water along the salinity gradient of the highly turbid macrotidal Gironde Estuary using a solid–liquid extraction. Uranium behaved conservatively whatever the water discharges observed. The slight dissolved U depletion compared to the theoretical dilution line between the fluvial and marine end-members occasionally observed in the low salinity range (0–3) was attributed to the mixing of different water bodies of the Gironde tributaries. In contrast, dissolved V behaviour was largely influenced by the hydrological conditions, showing increasingly pronounced addition with decreasing freshwater discharges, (i.e. increasing residence times of water and particles in the estuary). This addition of dissolved V in the low- to mid-salinity range was attributed to desorption processes observed in the Maximum Turbidity Zone (MTZ). The distribution of dissolved Mo concentrations along the salinity gradient was highly variable. Apparent conservative, and non-conservative behaviours were observed and were related to the concomitance of desorption from SPM, inputs from sediments for additive distribution and biological uptake and removal into sediments for subtractive distribution. Based on the whole database (2003–2007), annual net fluxes to the coastal ocean were estimated for dissolved U (15.5–16.6 t yr⁻¹) and V (31.3–36.7 t yr⁻¹).     

Trace metal composition of colloidal organic material in marine environments

Marine colloidal material (1 kDa–0.2 μm) was isolated by cross-flow ultrafiltration followed by diafiltration and freeze-drying from surface waters of the Gulf of Mexico and the Middle Atlantic Bight (MAB), as well as from estuarine waters of Galveston Bay. Elemental characterization of isolated colloidal material included organic carbon (OC) and selected trace metal (Cu, Pb, Zn, Cd, Co, Ni, Cr, Be, Fe, Al, Mn, V, Ba, and Ti) determinations. It was found that levels of these metals in marine colloids ranged from <0.1 to 50 μg/g colloidal matter, except for Fe which generally had a concentration >120 μg/g. Most metals (Cu, Pb, Zn, Ni, Al, Mn, V, and Ti) had an average concentration >1 μg/g while concentrations of Cd, Co and Be were usually <1 μg/g. Metal concentrations (μg/g) in isolated colloids were, in general, higher in Galveston Bay than in the Gulf of Mexico, suggesting either high abundance of trace metals in estuarine waters or differences in organic matter composition. Higher colloidal metal concentrations in the MAB than in the Gulf of Mexico might be due to higher terrestrial inputs in the MAB. Colloidal metal concentrations (μg/g) were generally lower than those in average soils, continental crust and suspended particles. However, metal/aluminum ratios (Me/Al) in isolated marine colloids were significantly higher than those for average soils and continental crust. Most importantly, colloids had a metal composition and metal/OC ratio (Me/C) similar to humic substances and marine plankton, suggesting that marine colloids largely originate from planktonic sources and are composed of predominately organic components. The Me/C ratios of Galveston Bay colloids followed the sequence of Cu>Ni, Cr, Zn>Mn>Co>Pb, Cd, which is similar to the Irving–Williams order except for Mn, suggesting that the interaction of metals with marine colloids is determined by the affinity of metals for specific organic ligands.     

The nematodes of the Thames estuary: Assemblage structure and biodiversity, with a test of Attrill's linear model

Although many studies of Nematoda have been undertaken in estuarine systems, there are relatively few studies which have analysed the distribution of fauna across the entire salinity range from marine to freshwater conditions. The Thames estuary has a long history of anthropogenic impact and recovery, since it was described as “azoic” in the 1950s, which has been monitored primarily through studies of water quality and fish stocks, with less emphasis on macroinfauna and very little information on meiofaunal organisms. This study aimed to describe the nematode fauna at eight stations along the estuary from marine to freshwater conditions in order to assess patterns of density, diversity and species assemblage structure. Nematode density and diversity were generally lower in the middle reaches of the estuary, associated with the region of greatest salinity range, a pattern which was found to be in agreement with Attrill's [2002. A testable linear model for diversity trends in estuaries. Journal of Animal Ecology 71, 262–269] linear model. Multivariate analysis confirmed that each station supported a distinct nematode fauna, which could be used to identify five zones along the estuary related to salinity regime. Although alpha diversity at each station was relatively low, species turnover along the estuary resulted in relatively high gamma diversity (153 spp.) similar to that found in a number of European estuaries. The results of this study did not suggest that the nematode fauna was under significant stress from the lower levels of pollution currently found in the system. The potential routes for the recovery and re-colonization of the estuary since it most polluted days are discussed.     

Seasonal phytoplankton composition, productivity and biomass in the Neuse River estuary, North Carolina

Phytoplankton community composition, productivity and biomass characteristics of the mesohaline lower Neuse River estuary were assessed monthly from May 1988 to February 1990. An incubation method which considered water-column mixing and variable light exposure was used to determine phytoplankton primary productivity. The summer productivity peaks in this shallow estuary were stimulated by increases in irradiance and temperature. However, dissolved inorganic nitrogen loading was the major factor controlling ultimate yearly production. Dynamic, unpredictable rainfall events determined magnitudes of seasonal production pulses through nitrogen loading, and helped determine phytoplankton species composition. Dinoflagellates occasionally bloomed but were otherwise present in moderate numbers; rainfall events produced large pulses of cryptomonads, and dry seasons and subsequent higher salinity led to dominance by small centric diatoms. Daily production was strongly correlated (r = 0·82) with nitrate concentration and inversely correlated (r = −0·73) with salinity, while nitrate and salinity were inversely correlated (r = −0·71), emphasizing the importance of freshwater input as a nutrient-loading source to the lower estuary. During 1989 mean daily areal phytoplankton production was 938 mgC m⁻², mean chlorophyll a was 11·8 mg m⁻³, and mean phytoplankton density was 1·56 × 10³ cells ml⁻¹. Estimated 1989 annual areal phytoplankton production for the lower estuary was 343 gC m⁻².     

Chemical forms of iron in the Connecticut River estuary

The ‘dissolved’ iron (that passed through a 0·4-μm filter) varied nonconservatively with salinity in the Connecticut River estuary. However, the total iron appeared to be conservative. Measurements of Fe(II) and Fe(III) showed that oxidation of Fe(II) was not a factor in the decrease of ‘dissolved’ iron in the low salinity region. A solubility model and analyses based on different pore-size filters indicated that a substantial amount of the ‘dissolved’ iron in the low salinity region was colloidal iron. The coagulation of fine colloidal particles led to the non-conservative behavior of ‘dissolved’ iron during estuarine mixing, but it did not necessarily lead to removal of total iron from the waters. Particulate iron was 80–90% of the total iron and it covaried with the total suspended matter during mixing and sediment resuspension. The residence time of water in the Connecticut River estuary was too short to allow removal of iron from the water column within the estuary.     

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.     

Aggregation of riverine colloidal iron in estuaries: A new kinetic study using stopped-flow mixing

The kinetics of aggregation of riverine colloidal iron have been examined using a stopped-flow technique which probes the first few seconds of mixing between river and sea water end members. A significant fraction, up to 80%, of the colloidal iron is aggregated during the first 1–2 s of mixing, indicating that the aggregation process is much faster than previously thought. Most of the aggregation induced by seawater results from the divalent cations Mg²⁺ and Ca²⁺, with the overall ionic strength having little influence. At equal concentrations of 27 mM, the rate of aggregation by alkaline earth cations increased with ionic size Mg²⁺ < Ca²⁺ < Sr²⁺ < Ba²⁺. The aggregation rates were indifferent to the anion (Cl⁻ or SO₄²⁻) present. Very high aggregation rates were also induced by the common water treatment coagulant Al₂(SO₄)₃ at concentrations in the range 20–30 µM Al(III), several orders of magnitude lower that those used for the seawater cations. Our results support the view that specific chemical interactions between the cations and the colloid particle surface, rather than simple electrical effects, control the colloid stability.     

Geochemical cycling in the Hooghly estuary, India

U–Th decay series isotopes, δ¹⁸O and Si measurements in the river estuarine waters and sediments of the polluted Hooghly estuary as well as the surface waters of the Bay of Bengal, its high salinity end member, are reported. Dissolved Si indicates that there are probably two mixing regimes, dissolved U behaviour is nonconservative and δ¹⁸O behaves conservatively in the overall estuarine region. Isotopes of reactive elements, viz. ²³⁴Th and ²¹⁰Po, are removed from the estuarine waters in <2 days and <1 month, respectively, which is due to high suspended matter (30–301 mg l⁻¹). ²²⁸Ra and ²²⁶Ra are profusely released into the estuarine waters in the low to mid-salinity regions.As expected, the opposite trend is observed in the case of estuarine sediments and suspended matter. Reactive isotopes of Th, ²¹⁰Pb and ²¹⁰Po are enriched, whereas Ra isotopes are depleted with respect to their parent nuclides in the estuarine sediments and suspended matter. ²³²Th/Al ratio appears well suited to study the distribution and mixing of the bed load sediments of the Ganga–Brahmaputra (G–B) and the Hooghly rivers with those from other rivers on the Bay of Bengal floor.     

Salinity tolerance of northern Brazilian mangrove crab larvae, Ucides cordatus (Ocypodidae): Necessity for larval export?

The life cycle of the semiterrestrial mangrove crab Ucides cordatus includes pelagic larvae that are released into estuarine waters during the wet season and who may thus encounter potentially stressful low and variable salinity conditions. The effect of salinity on the survival of the zoea larvae, the number of zoeal stages and the duration of development from hatching to megalopa was experimentally studied by rearing larvae from the Caeté estuary, Northern Brazil, in seven salinity treatments (0, 5, 10, 15, 20, 25, and 30). For a better interpretation of the laboratory results, estuarine salinities were measured over five consecutive years during the species' reproductive season. The survival of the zoea larvae varied significantly with salinity, while the number of stages and the duration of their development remained constant. Development to megalopa took 20.77 ± 1.57 days and comprised five zoeal stages with ZI and ZII being euryhaline and later stages stenohaline. The newly hatched larvae stayed alive for up to 6 days in freshwater (average 4.32 ± 0.82 days), but did not moult to the second zoeal stage. ZII larvae first occurred from salinity 5 onwards and later zoeal stages at all tested salinities ≥10. However, the larvae only survived to megalopa at salinities ≥15, with highest numbers at salinity 30 (72%) and lowest at 15 (16%). Lethal salinities ≤10 occurred frequently in the estuary during the reproductive season. This suggests a need for larval export to offshore and thus more saline waters to allow for significant larval survival and maintenance of viable populations of this commercially important species. A regional rather than local approach for management is suggested due to the likelihood of long distance larval dispersal by offshore currents.     

Shelf spawning habitat of Emmelichthys nitidus in south-eastern Australia – Implications and suitability for egg-based biomass estimation

The spawning habitat of Emmelichthys nitidus (Emmelichthyidae) in south-eastern Australia is described from vertical ichthyoplankton samples collected along the shelf region off eastern through to south-western Tasmania during peak spawning in October 2005–06. Surveys covered eastern waters in 2005 (38.8–43.5°S), and both eastern and southern waters in 2006 (40.5°S around to 43.5°S off the south-west). Eggs (n = 10,393) and larvae (n = 378) occurred along eastern Tasmania in both years but were rare along southern waters south and westwards of 43.5°S in 2006. Peak egg abundances (1950–2640 per m⁻²) were obtained off north-eastern Tasmania (40.5–41.5°S) between the shelf break and 2.5 nm inshore from the break. Eggs were up to 5-days old, while nearly 95% of larvae were at the early preflexion stage, i.e. close to newly emerged. Average abundances of aged eggs pooled across each survey declined steadily from day-1 to day-5 eggs both in 2005 (97-18) and 2006 (175-34). Moreover, day-1 egg abundances were significantly greater 2.5 nm at either side of the break, including at the break, than in waters ≥5 nm both inshore and offshore from the break. These results, complemented with egg and larval data obtained in shelf waters off New South Wales (NSW; 35.0–37.7°S) in October 2002–03, indicate that the main spawning area of E. nitidus in south-eastern Australia lies between 35.5°S off southern NSW and 43.5°S off south-eastern Tasmania, and that spawning activity declines abruptly south and westwards of 43.5°S around to the south-west coast. In addition, quotient analyses of day-1 egg abundances point to a preferred spawning habitat contained predominantly within a 5 nm corridor along the shelf break, where waters are 125–325 m deep and median temperatures 13.5–14.0 °C. Spawning off eastern Tasmania is timed with the productivity outburst typical of the region during the austral spring, and the temperature increase from the mixing between the southwards advancing, warm East Australian Current and cooler subantarctic water over the shelf. Overall, ichthyoplankton data, coupled with reproductive information from adults trawled off Tasmania, indicate that E. nitidus constitutes a suitable species for the application of the daily egg production method (DEPM) to estimate spawning biomass. This finding, together with evidence in support of a discrete eastern spawning stock extending from southern NSW to southern Tasmania, strengthens the need for DEPM-based biomass estimates of E. nitidus prior to further fishery expansion.     

The Significance of Diagenesis versus Riverine Input in Contributing to the Sediment Geochemical Matrix of Iron and Manganese in an Intertidal Region

Summer porewater and spring and summer surficial sediment samples were collected from 26 locations in the intertidal region of the Fraser River estuary. Porewaters were analysed for dissolved iron and manganese (as defined by species <0·2μm in diameter) to assess the contribution of diagenesis to concentrations of iron and manganese oxides at the sediment–water interface. Surficial sediment samples were geochemically characterized as: % organic matter (% LOI); reducible iron (RED Fe, iron oxides) and easily reducible manganese (ER Mn, manganese oxides). Grain size at each site was also determined. The sediment geochemical matrix, as defined by the above four parameters, was highly heterogeneous throughout the intertidal region (three-way ANOVA;P<0·0001). For RED Fe and ER Mn, this heterogeneity could be explained by either diagenetic processes (RED Fe) or by a combination of the proximity of the sample sites to the mouth of the Fraser River estuary plus diagenetic processes (ER Mn). Correlation (Spearman Rank Correlation Test (r_s), of dissolved iron within the subsurface sediments with amounts of RED Fe recovered from the associated surface sediments was highly significant (r_s=0·80, P<0·0001); high concentrations of RED Fe at the sediment–water interface co-occurred with high concentrations of dissolved iron, regardless of the proximity of the sample locations to riverine input. Compared with iron, the relationship between dissolved manganese and ER Mn from surface sediments was lower (r_s=0·58;P<0·0008). Locations most strongly influenced by the Fraser River contained greater concentrations of ER Mn at the sediment–water interface than that which would be expected based on the contribution from diagenesis alone. Sediment grain size and organic matter were also influenced by the proximity to riverine input. Surficial sediment of sites close to the river mouth were comprised primarily of percent silt (2·0μm–50μm) whereas sites not influenced by riverine input were primarily percent sand (grain size >50μm). Concentrations of organic matter declined from the mouth to the foreslope of the estuary. With the exception of RED Fe, temporal variation (May vs July) was insignificant (P>0·05, three-way ANOVA). Concentrations of RED Fe recovered from the surficial sediments were in general greater in the summer vs spring months, although spring and summer values were highly correlated (Pearson Product Moment Correlation Coefficient; PPCC; R=0·89;P<0·0001). As the bioavailability of metals is dependent on sediment geochemistry, availability throughout the intertidal region will also be spatially dependent. This heterogeneity needs to be taken into account in studies addressing the impact of metals on estuarine systems.