Concentrations and transport of trace metals in the St. Lawrence River

Samples of raw water were collected in the St. Lawrence River during six sampling trips from August 1990 to April 1992. Water samples were analyzed for both dissolved and particulate phases for five trace metals. Partition coefficients (Kd) and metal fluxes were calculated in order to determine metal transport. A mass balance equation was used for the determination of the major metal sources to the St. Lawrence River and an estimation of metal loadings to the estuary was made. Average dissolved metal concentrations were found to be Cd 10 ng/L, Co 74 ng/L, Cu 64 ng/L, Fe 69 µg/L and Mn 700 ng/L. Particulate concentrations were (in µg/g) 1.68 for Cd, 31 for Co, 73 for Cu, 25 mg/g for Fe and 1.69 mg/g for Mn. Co, Fe and Mn were transported essentially in the particulate phase while Cd and Cu were predominantly found in the dissolved phase at 56% and 48% of the total metal concentration respectively. Log Kd values varied from 5.1 (for Cu) to 6.8 (for Mn). In the dissolved phase the major sources were found to be the Great Lakes and the Ottawa River whereas in the particulate phase Québec tributaries appear to be the most important. Industrial inputs are quite important in both the dissolved and the particulate phases for Cd, whereas other sources are very variable, especially for the dissolved phase.     

Seasonal variations in the cycling of aluminium,cadmium and manganese in a Scottish sea loch: biogeochemical processes involving suspended particles

Concentrations of Al, Cd and Mn were determined in water and particles collected from water bottles over one year during 19 surveys of a silled fjord. Nutrient and hydrographic data were also collected. Particle fluxes were determined at one site using a sediment trap array. Concentrations of dissolved Al showed the strongest (negative) relationship to salinity (r=0.91). This correlation decreased with the onset of the diatom bloom and was insignificant immediately post bloom. Removal of dissolved Al was coincident with an increase in particulate Al concentrations. The degree of removal could be predicted from previously reported Al/Si uptake ratios. Concentrations of leachable P in particulate material from the sediment traps increase at the onset of the bloom and decrease coincident with rapid regeneration as the bloom crashed. Particulate leachable Cd showed a lag in apparent uptake and regeneration relative to particulate leachable P. A substantial amount (ca. 53%) of the annual particle flux of Mn to the deepest trap is material recycled at the sediment surface and is not accumulated in the bottom sediment. Dissolved and particulate Mn levels in the loch have a strong seasonal pattern with low values prior to the spring phytoplankton bloom and increased values after the bloom crash. Maximum concentrations were observed in late autumn. Levels decreased to near pre-bloom values early the following year. This suggests bacterial decay of deposited organic carbon associated with the spring bloom-maintained suboxic conditions at or near the seawater-sediment interface throughout the majority of the year. After exhaustion of this organic matter pool recycling ceased for a brief (2–3 months) winter period.     

Dissolved and particulate trace metals in a Scottish sea loch: an example of a pristine environment?

In the near pristine environment of a silled fjord on the west coast of Scotland samples were taken for the determination of dissolved and particulate trace metals (Fe, Mn, Cu, Ni, Cd, Zn and Pb), together with nutrient and hydrographic data, during 19 surveys carried out over a year. An indication of the pristine nature of the environment are the low concentrations of dissolved silicon, phosphate and nitrate which are considerably lower than those of coastal waters which are subject to larger anthropogenic burdens. Distributions of dissolved Cu, Ni and Cd were found to broadly reflect conservative mixing of freshwater and seawater with both end members having similar concentrations. The concentration of dissolved Cu and Ni in seawater entering upper Loch Linnhe (Cu 0.28 μg l⁻¹; Ni 0.26 μg l⁻¹) was consistent with the 1:1 conservative mix of Irish Sea water and North Atlantic surface water predicted from radio-caesium tracer experiments (Mackay & Baxter, 1985). Atmospheric input of trace metals to upper Loch Linnhe appeared to be a relatively minor term in the mass balance relative to fluvial inputs. Values of distribution coefficients Kd were similar to those previously reported for the coastal environment. Iron showed the strongest affinity for the suspended sediments; with particulate percentages of the total load usually greater than 80%. Lead and Mn showed a similar strong affinity to the particle phase. For Cu, Ni and Zn the mass of the element in the dissolved phase was generally greater than that in the particulate fraction. Cadmium, was least associated with the particles, with typically greater than 90% existing in the dissolved phase.     

The speciation of dissolved copper,cadmium and zinc in Manila Bay,Philippines

At present, there is a very limited information on the levels and distribution of dissolved metals in Manila Bay. In this study, the horizontal and vertical distribution of operationally defined species (labile, bound and total) of dissolved copper (Cu), cadmium (Cd) and zinc (Zn) were determined using differential pulse anodic and cathodic stripping voltammetry in water samples obtained from 18 stations in November 1998. In addition, the 24-h variability in the concentrations of these species at different depths in the water column was determined. These measurements were complemented by the determination of temperature, salinity, dissolved oxygen, chlorophyll a, particulate organic carbon and nutrients. Results showed that more than 50% of total dissolved copper and cadmium were labile while 50% of total dissolved zinc was organically bound. Vertical profiles showed that Cu, Cd and Zn concentrations were generally high at the surface. Zinc and cadmium were characterised by the presence of a mid-depth minimum while copper did not show any clear vertical trend.

Dissolved Cu concentrations during the spatial and diurnal samplings ranged from 0.32 to 6.95 nM and 1.52 to 45.65 nM, respectively. For Cd, the concentrations in 18 stations ranged from 0.05 to 2.92 nM, and from 0.03 to 2.42 nM over a 24-h period. Zn concentrations ranged from 2.48 to 147.43 nM and 2.87 to 88.27 nM during the spatial and diurnal samplings, respectively. The large variation in the concentration of Cu, Cd and Zn in the bay was observed to be associated with the presence of a large vertical density gradient in the water column, which appeared to limit the exchange of materials between the surface and bottom waters. Elevated levels of these metals near point sources suggest anthropogenic inputs in the bay.     

Mercury distribution in Douro estuary (Portugal)

Determinations of dissolved reactive and total dissolved mercury, particulate and sedimentary mercury, dissolved organic carbon (DOC), particulate organic carbon (POC) and suspended particulate matter (SPM) have been made in the estuary of river Douro, in northern Portugal. The estuary was stratified by salinity along most of its length, it had low concentrations of SPM, typically <20 mg dm(-3), and concentrations of DOC in the range <1.0-1.8 mg dm(-3). The surface waters had a maximum dissolved concentration of reactive mercury of about 10 ng dm(-3), whereas for the more saline bottom waters it was about 65 ng dm(-3). The surface waters had maximum concentrations of total suspended particulate mercury of approximately 7 microg g(-1) and the bottom waters were always <1 microg g(-1). Concentrations of mercury in sediments was low and in the range from 0.06 to 0.18 microg g(-1). The transport of mercury in surface waters was mainly associated with organic-rich particulate matter, while in bottom waters the dissolved phase transport of mercury is more important. Lower particulate organic matter, formation of chlorocomplexes in more saline waters and eventually the presence of colloids appear to explain the difference of mercury partitioning in Douro estuarine waters.     

Distributions and removal fluxes of trace metals in the water column of the Hung-Tsai Trough off southwestern Taiwan

Vertical profiles of dissolved and particulate Mn, Fe, Ni, Cu, Zn, Cd, Pb, and (234)Th were determined in the Hung-Tsai Trough off southwestern Taiwan during 19-23 November, 2004. Except in the case of Cd, the distribution coefficient (K(d)) of the trace elements showed a negative correlation with the suspended particle concentration. Based on the average K(d) values, the general sequence of particle affinities for the eight trace elements is, from highest to lowest, Fe>Mn≈Pb>Zn≈Th>Cd≈Cu≈Ni. The trace metal data was coupled with the particle removal flux estimated from (234)Th/(238)U disequilibrium to investigate metal removal by particle sinking from the euphotic layer. The residence time of trace elements with respect to particle removal from the euphotic layer was estimated. A negative correlation between the residence time and the distribution coefficient for the trace metals was found.     

Speciation of organic carbon,Cu and Mn in the River Marne (France): the role of colloids

The distribution of organic carbon (OC) and of some metals (Cu, Mn) amongst the particulate (>0·2 μm), colloidal (10 kDa–0·2 μm) and the truly dissolved (<10 kDa) fractions of the River Marne was investigated during the phytoplankton spring bloom. A tangential ultrafiltration (UF) device was utilized to separate the colloidal fraction. On average, 22% of the OC, 31% of the Cu and 53% of the Mn, usually assigned to the so‐called dissolved fraction, were found in the colloidal fraction. The colloidal fraction exhibited a behaviour different from that of the particulate and truly dissolved fractions. Autochthonous production led to enrichment in the colloidal and particulate OC pools: up to 47% of the total dissolved OC was in the colloidal fraction. An increase in the colloidal metal fraction, concomitant with a fall in the truly dissolved fraction, coincided with peaks in phytoplankton during the bloom. These phenomena might be related either to an increase in pH associated with photosynthetic activity, resulting in the precipitation of truly dissolved forms into the colloidal fraction, or to scavenging of the truly dissolved metals by the algal species of colloidal size. The interaction between the colloidal and the truly dissolved phases was very important. The partition coefficients of the Cu and Mn between the colloidal and truly dissolved fractions were higher than between the particulate and the truly dissolved fractions. This pattern is consistent with a greater specific surface area of colloids than macroparticles. Consequently, the adsorption and complexation capacities are enhanced in the colloidal fraction of the particulate matter. The extraction of hydrophobic complexes with Cu using C₁₈ Sep‐Pak columns, showed that the Cu occurring in colloidal, total dissolved or truly dissolved forms was significantly complexed by the organic matter. The truly dissolved fraction might be complexed up to 100% during a phytoplankton bloom. Copyright © 1999 John Wiley & Sons, Ltd.     

Trace metals in the northern North Sea

Cadmium, lead and copper have been determined in the dissolved and particulate phase for surface waters of the northern North Sea. Dissolved cadmium and copper show concentration gradients associated with salinity fronts which mark the boundary between coastal and ocean waters; lead does not. The particulate phase is shown to represent only a small fraction of the total metal concentration. Processes likely to be responsible for the observed distribution are discussed.     

Distribution and fluxes of metals in the St. Lawrence River from the outflow of Lake Ontario to Québec City

Six anchor stations in the St. Lawrence River from the outflow of Lake Ontario to Quebec City, were occupied for ca. 24 hours in June 1987 during low flow conditions. Samples of water and suspended particulate matter were separated by continuous-flow centrifugation, and were collected every two hours.During this sampling period, fluxes of dissolved forms of zinc, copper and nickel increased in Lac St. François and downstream relative to the sum of the fluxes for the two upstream stations at the outflow of Lake Ontario. Increases in the flux of dissolved zinc and copper were pronounced below Montreal and above Lac St. Pierre. For particulate forms of metals, all five metals show that there are significant inputs in the section of the St. Lawrence River between Lac St. François and the station just above the entrance to Lac St. Pierre.The average concentrations of dissolved cadmium, lead, zinc, copper and nickel ranged from 7–23 ng/l; 9–35 ng/l; 0.434–0.939 g/l; 0.15–0.89 g/l and 0.58–1.12 g/l respectively.Regression analysis of the dissolved and particulate metal concentrations suggests that the concentration of dissolved cadmium, lead, zinc and nickel can be predicted from the regression equation and the determination of particulate metal concentration. This prediction appears to be independent of the suspended particulate matter concentration which varies from ca. 1 to 10 mg/l from the outflow of Lake Ontario to Québec City.     

Phosphorus Forms and Their Changes in Water of Three Subalpine Lakes in Italy

Total phosphorus and its main forms: dissolved mineral, dissolved organic, particulate organic and particulate mineral in the vertical water column of three subalpine lakes of various types in Italy, has been estimated during the winter-vernal season. The range of variation in the phosphorus content in these waters was as follows: total phosphorus 16 ± 2860 μg/1 PO₄, dissolved mineral phosphorus 4 ± 1040 μg/l PO₄, dissolved organic phosphorus 1 ± 160μg/l PO₄, particulate organic phosphorus 0 ± 290 μg/l PO₄ and particulate mineral phosphorus 1 ± 100 μg/l PO₄, Generally the content of total phosphorus and dissolved mineral phosphorus (phosphates) increased with the degree of eutrophy with the depth and with the progress of the vernal season towards the summer stagnation time. The amount of phosphates increased in water with the depletion of oxygen, both in the verical water column and with the progress of stagnation time. The amounts of dissolved organic phosphorus decressed with the depth of the vertical water column whereas the dissolved mineral phosphorus increased. The development of the particulate organic phosphorus stratification in the vertical water column was clearly visible in the eutrophic lake. The quantities of total phosphorus and its main component, dissolved mineral phosphorus, decreased evidently from January to May in all three lakes, mostly in the eutrophic lake. The reason of this decrease is sorption by lake sediments and to a certain degree sedimentation of phosphorus sorbed by ferric hydroxide. The increase of dissolved mineral phosphorus and that of total phosphorus in the vertical water column and with the progress of summer stagnation had as a reason the liberation of phosphorus from sediments, and not so much decomposition of sedimentating plankton or dissolved organic phosphorus. The share of single (mean) values of phosphorus forms in the total phosphorus was as follows: In the oligotrophic lake the share of particulate mineral phosphorus was extremely high in March (21% of the total), probably because of the inflow of the melting waters from the drainage area. The development of vertical stratification in waters of three subalpine Italian lakes at the end of the vernal season (May) indicates the quantitative prevailing of dissolved mineral phosphorus with its increase with the depth and domination of dissolved organic phosphorus in the trophogenic zone.     

Dissolved and particulate trace metal fluxes through the central English Channel, and the influence of coastal gyres

Measurements of dissolved Cd, Co, Cu, Mn, Ni, Pb, and Zn have been made on a seasonal basis at five stations on a north–south transect across the central English Channel between Cherbourg and the Isle of Wight. Vertical and horizontal distributions of dissolved Cd, Pb, Cu and Zn are relatively uniform except for sampling sites near the English coast. Dissolved Mn and Co show increased concentrations in the English coastal waters, and for Mn the seasonal trend in concentration follows the pattern seen in the Strait of Dover with higher values in the late summer. Ni and Cu are higher in concentration on the English side, which reflects mainly riverine sources. Measurements were also made of particulate forms of the metals above plus particulate Al, Ca, Fe, Mg, Sr and Ti. Water column concentrations of particulate metals broadly follow the distribution of suspended particulate matter, with highest concentrations near the UK coast. Trace metal concentrations have been integrated with modelled data on fluxes of water to provide estimates of fluxes for these elements into the eastern Channel, and an initial comparison is made with data for fluxes of metals through the Strait of Dover obtained during an earlier study. A major influence on the fluxes of particulate metals through the Isle of Wight-Cherbourg transect is the gyre system to the South east to the Isle of Wight, which has important east to west as well as west to east transport components. For those elements where the dissolved form of the metal dominates, the large flow of water in the central Channel waters leads to major fluxes of the metals towards the east and the Strait of Dover. However, the high suspended particulate matter loadings in the coastal waters and impact of the gyre system lead to net east to west fluxes of particulate Al, Fe, Mn and Ti. Comparison of these fluxes with data on the net west to east transport of these materials through the Strait of Dover infers that there must be a significant supply of these particulate metals to the eastern Channel.     

Dynamics of particulate major and trace elements in the lower reaches of the Daugava River and adjacent area of the Gulf of Riga (Baltic Sea)

Suspended particulate matter (SPM) was collected in the freshwater-seawater mixing zone in the lower reaches of the Daugava River (Latvia) and adjacent marine area, during five cruises in 1998-2001. The study focused on biogeochemical phase exchange processes. SPM in the freshwater was found to be mainly allochthonous with a high content of organic matter, Mn and sorbed phosphate. Property-salinity plots suggested flocculation of humic-Fe complexes across the salinity gradient. The variability of sorbed phosphate was related to particulate Fe, although no dependence on pH and ionic strength was observed. The Mn contents of SPM mainly follow conservative mixing, but there are also indications of interface exchange of Mn in the mixing zone. The geochemical behaviour of particulate Al appears to differ from that of Fe. In early spring, trace element contents in SPM (Cr, Ni, Cu, Zn, Cd, Pb) correlate tightly with particulate organic matter, whose distribution is linked to phytoplankton distributions.     

The Role of Particulate Matter in the Mobilization of Trace Metals during Anaerobic Digestion of Solid Waste Material Die Bedeutung der partikulären Substanz für die Mobilisierung von Spurenmetallen beim anaeroben Abbau fester Abfallstoffe

Metal ions bound to particulate matter represent the greatest portion (i.e. > 95%) of the total metal content found in leachate from reactor experiments where solid waste material was anaerobically digested. This seems true even though strong complexing agents are in solution which increase the solubility of Pb and Cu by a factor up to 10⁴… 10⁵ over that theoretically predicted according to the solubility of the corresponding sulfide mineral. A titrimetric characterization of the metal ion binding sites of the particulate matter suggests that the metal binding properties of the particulate matter are mainly due to organic, aminoacid-type compounds (amines. thio groups, carboxylic groups) probably of bacterial origin. The change of the concentration of the binding sites with time, together with the change of the composition of the particulate matter indicates that bacterial flocs are suspended in the leachate during the switch from acidogenic to methanogenic conditions — either due to the detachment of bacterial films from the solid material by the intensive gas production or due to the formation of syntrophic methanogenic bacterial associations or a combination of both. A combination of the two factors, strong affinity of bacterial mass to metal ions on the one hand, and suspending of the bacterial mass in the leachate on the other hand, will therefore imply a great mobilizing potential for trace metals. Consequently, the highest concentrations of particulate bound Cd were found in reactor experiments where sewage sludge contaminated with Cd was added to the waste material. An increase of the concentration of dissolved cadmium over the solubility of cadmium sulfide, however, could not be observed.     

Dissolved and particulate trace metals in meltwater from the Rhône glacier

Glacial meltwater and sediment at the source of the River Rhône have been analyzed to determine: 1. the partitioning of Al, Cd, Co, Cu, Cr. Fe, Mn, Ni, Pb and Zn between the water and particulate phase. 2. the particle size ranges which affect the dissolved trace metal ion composition of the meltwater and 3. the availability (potential release) of the ten trace metal ions from the sediment. Greater than 80% of the total Cd, Cu, Mn, Ni and Zn were found to be in operationally-defined (0.4 μm) dissolved forms. Fe and Al in the meltwater are primarily associated with particles in the size range 0.4–8 μm, while Cd. Cu, Mn, Ni and Zn occur with particles smaller than 0.1 μm. For the sediment, Cu, Ni and Pb were significantly present as exchangeable forms; only Cu, Ni, Pb and Zn were determined as organicallybound forms.     

Dissolved trace metal distributions in Port Jackson estuary (Sydney Harbour), Australia

Concentrations of dissolved metals (Cd, Cu, Ni, Mn and Zn) were determined for summer and winter, under low-flow conditions in Port Jackson, a microtidal, well-mixed estuary in south-east Australia. Mean concentrations of Cd (0.04+/-0.02 microg/l), Ni (0.86+/-0.40 microg/l), Mn (20.0+/-25 microg/l) and Zn (6.47+/-2.0 microg/l) were below water quality guidelines. Concentrations of Cu (1.68+/-0.37 microg/l), however, slightly exceeded recommended values. Dissolved Ni and Mn behaved mostly conservatively, whereas Cd, Cu and Zn showed mid-estuarine maxima. Peaks in Cd, Cu and Zn concentrations were located in the upper estuary, independent of the salinity and suspended particulate matter loading, and were consistent with anthropogenic inputs of metals in the estuary. Concentrations of dissolved Cu were highest in summer, whereas concentrations of Cd, Ni and Mn were significantly lower in summer than winter (P< or =0.05). The increase in temperature and biological activity during summer explained the seasonal variation. The sequence of log K(d) values (20-30 salinity) was Mn>Zn>Cu>Ni. These results give unique information concerning the contemporaneous distribution of dissolved trace metals in the Port Jackson estuary and they provide a data set against which the long-term contamination may be assessed.     

新疆博斯腾湖水体颗粒和溶解有机碳的季节变化及其来源初探

在博斯腾湖选取了13个点位,于2012年5、8、10月测定表层和底层水体中的颗粒有机碳、溶解有机碳、颗粒有机氮和叶绿素a含量.结果显示颗粒和溶解有机碳在表层水体中的浓度与底层相近.博斯腾湖水体中颗粒有机碳的季节变化十分明显,其平均浓度从春季(0.64 mg/L)到夏季(0.71 mg/L)变化不大,但在秋季变化十分显著(浓度达1.58 mg/L).其中西北湖区和湖心区颗粒有机碳的季节变化最明显,东部湖区颗粒有机碳的季节变化相对较小.博斯腾湖水体的颗粒有机碳在春、秋两季主要来自外源输入,在夏季受水体中浮游生物的影响较大.博斯腾湖水体中溶解有机碳也具有一定的季节变化,夏季浓度(平均为9.3 mg/L)略低于春、秋两季(平均为10.3 mg/L).溶解有机碳在河口区的季节变化最强,其夏季浓度明显偏低,主要是由于开都河河水的稀释作用.总体上,博斯腾湖水体中溶解有机碳浓度的变化主要受外部因素的影响.     

Variability of particulate (SS,POC) and dissolved (DOC,NO3) matter during storm events in the Alegria agricultural watershed

The temporal variability of suspended sediment, nitrates (NO₃) and dissolved (DOC) and particulate organic carbon concentrations was analysed in the Alegria agricultural watershed over a 2‐year period. Nine storm events were studied, including an exhaustive analysis of hydrometeorological conditions, quantification of fluxes, and concentration‐discharge hysteresis loop characterization. The overall aim was to study the variability in these components during storm events and determine the mechanisms (flow paths) affecting the trajectories, from the source to the stream. The forms, rotational patterns and trends of hysteretic loops were investigated, and relationships between hysteresis features and hydrological parameters were studied. The results revealed clear differences between particulate (suspended sediment, particulate organic carbon) and dissolved (DOC, NO₃) matter transport responses. Movement of the particulate matter was attributed to surface water, as reflected in clockwise hysteresis loops, whereas dissolved matter showed, in general, counterclockwise hysteresis loops, indicating a time delay in the arrival of solutes to the stream. This could be related to subsurface flow paths for DOC and a groundwater source for NO₃. Copyright © 2013 John Wiley & Sons, Ltd.     

Organic carbon release by phytoplankton and bacterial reassimilation

The release of organic carbon by phytoplankton and its reassimilation by bacteria were studied in Lake Geneva during four daily kinetics, using¹⁴C techniques. Gentamycin was used to suppress bacterial activity. Size fractionation was used to measure¹⁴C fixation in 2 particulate fractions (≥1 μm and 0.2 to 1 μm) and in a third fraction: dissolved organic carbon. Measurements of bacterial biomass and¹⁴C glucose uptake as the H¹⁴CO ₃ ⁻ uptake by samples prefractionated before incubation showed that the whole algae were retained on 1 μm pore size Nuclepore filters, but bacteria were retained on 1 μm and 0.2 μm filters. Concentration of 20 μg.ml⁻¹ gentamycin resulted in incomplete bacterial inhibition while phytoplankton was affected. Phytoplankton released less of 20% of its photoassimilated carbon of which a large proportion was utilized by bacterioplankton.     

Space-time variations of river water chemistry in RF southern Far East

Concentrations and seasonal variations of water chemistry, including dissolved and particulate forms of Fe, Mn, Zn, Cu, Pb, Cd, and Ni in rivers of Primorskii Krai are determined. It is shown that, unlike the macrocomposition, the effect of hydrological regime on the concentration of dissolved metal forms is controversial and depends on anthropogenic load, watershed landscapes, and pH variations. Elevated concentrations of dissolved metal forms are recorded in the beginning of spring flood and during low-water period. Beyond the limits of local impact of wastewater, the concentrations of dissolved forms of Cu, Zn, Ni, Pb, and Cd in river waters of the region insignificantly differ from the clearest rivers of the World.