Copper, lead and cadmium in coastal waters of the western North Sea

Cadmium, lead and copper have been determined in both dissolved and particulate phases for 130 surface-water samples from the coastal zone of Scotland and England in the western North Sea. The concentrations reported are, in general, lower than those published previously for the same area.The distribution of total metal concentration between the dissolved and particulate phases varies for the three elements. The lead distribution is dominated by its associations with particulate material while cadmium shows the reverse behaviour, existing almost totally in the dissolved phase. Copper is intermediate in behaviour, with the dissolved phase generally being dominant.An inverse relationship between salinity and dissolved copper concentration suggests a freshwater origin for this element. It is suggested that sedimentary and/or anthropogenic sources affect dissolved copper concentrations in coastal waters. The dissolved lead distribution reveals plumes of contaminated coastal water. The lead distribution is, however, dominated by associations with particulate material and sediments which produce a sharp concentration gradient close to the coast. The Humber estuary is identified as a significant source of cadmium to the North Sea.     

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Cadmium, lead and copper have been determined in both dissolved and particulate phases for 130 surface-water samples from the coastal zone of Scotland and England in the western North Sea. The concentrations reported are, in general, lower than those published previously for the same area.The distribution of total metal concentration between the dissolved and particulate phases varies for the three elements. The lead distribution is dominated by its associations with particulate material while cadmium shows the reverse behaviour, existing almost totally in the dissolved phase. Copper is intermediate in behaviour, with the dissolved phase generally being dominant.An inverse relationship between salinity and dissolved copper concentration suggests a freshwater origin for this element. It is suggested that sedimentary and/or anthropogenic sources affect dissolved copper concentrations in coastal waters. The dissolved lead distribution reveals plumes of contaminated coastal water. The lead distribution is, however, dominated by associations with particulate material and sediments which produce a sharp concentration gradient close to the coast. The Humber estuary is identified as a significant source of cadmium to the North Sea.     

Marine geochemistry of cadmium

A detailed study of particulate and dissolved cadmium distributions on 83 seawater samples from six profiles in the open North Atlantic Ocean showed a relatively homogenous distribution. The mean concentration of cadmium was 60 ± 27 ng/kg and the median concentration of particulate cadmium was 0.2 ng/kg. Although there are regional differences in dissolved cadmium concentrations among stations, it is suggested that cadmium behaves essentially as an inert element in sea water.Particulate cadmium is enriched by about a factor of four in samples from less than 400 m compared to samples from deeper than 1000 m. The high concentrations in surface waters are suggested to be due to aeolian transport of anthropogenically derived cadmium.Additional analyses of cadmium in the Gulf of Maine show a mean value of 230 ng/kg. The higher values in the Gulf of Maine are ascribed to the influence of continental runoff. Twelve sediment samples from the open North Atlantic show a relatively homogenous distribution, ranging from 0.13 to 0.21 ppm on a dry-weight basis.     

Release of cadmium in the Danube estuary: contribution of physical and chemical processes as determined by an experimental approach

The behavior of dissolved cadmium (Cd) in the Danube estuary was investigated through field sampling and mixing experiments using Danube River water and Black Sea water. The experiments were performed by mixing these two end-member waters in various proportions, with the addition of stable or radioactive Cd to the freshwater Danube end-member prior to the mixing. The release of Cd that resulted in maximum concentrations under field conditions was well simulated by mixing experiments. The experimental results were modeled assuming that the release of Cd was the sum of the contribution of physical effects resulting from dilution effects and the contribution of chemical effects resulting from dissolved Cd-complex formation (and isotopic exchange when concerned). In the absence of dissolved Cd-complexing ligands, the release of Cd due to the dilution of the particulate phase during mixing could explain part of the maximum concentrations observed in field conditions. Kinetic effects were established by comparing the theoretical and measured contribution of chemical effects resulting from dissolved Cd-complex formation. The non-equilibrium state observed during the mixing experiment suggested the presence of particulate labile Cd that was not easily mobilized. All these features supported the hypothesis that Cd released in estuaries is controlled both by the dilution of the particulate phase and by kinetic competitive complexation between particulate ligands (covering a large spectrum of nature and strength) and dissolved ligands.     

Precipitation of heavy metals in produced water: influence on contaminant transport and toxicity

Produced water undergoes changes in its physical chemistry including precipitation of heavy metals after being discharged and mixed with ambient seawater. Potential impacts of the precipitation of heavy metals on their transport and toxicity were studied using samples from offshore oil production sites on the Scotian Shelf off eastern Canada. Concentrations of aluminum, cadmium, chromium, cobalt, copper, iron, lead, manganese, nickel and zinc were measured in total, particulate and dissolved fractions together with Microtox tests for assessment of toxicity. Heavy metals in produced water were transformed from dissolved to particulate phase in a period of hours under oxygenated conditions, and aggregated to larger particles that settle rapidly (>100 m/day) over a few days. In addition, there was production of buoyant particles comprised of heavy metal precipitates sequestered onto oil droplets that were transported to the surface. The particulate fraction was generally more toxic than the dissolved fraction. This was evident at the mixing interface between produced water and seawater where elevated particulate and toxicity levels were observed. Laboratory studies suggest an increase in the toxicity of discharged produced water over time. Time-series experiments showed a sustained toxic response for more than a week following the oxidation of freshly discharged produced water that initially elicited little or no toxic response in the Microtox test. Chemical processes identified in this study, namely precipitation of heavy metals and consequent settling and rising fluxes of particles, will influence the toxicity, the fate and the transport of potential contaminants in the produced water. Therefore, these processes need to be considered in assessment of the environmental impact associated with offshore oil and gas operations.     

海水悬浮颗粒物中不同形态磷的测定

分别采用硫酸过硫酸钾作为氧化剂进行高压消解和用浓度为1 mol/dm³盐酸浸泡提取,然后用磷钼蓝分光光度法测定海水悬浮颗粒物、沉积物中的总磷和无机磷,用差减法得到有机磷。悬浮颗粒物总磷(PTP)和无机磷(PIP)质量浓度分别为(632.4～651.7)×10^-6和(436.6～452.6)×10^-6时,其相对标准偏差小于1.44%。悬浮颗粒物总磷、无机磷和有机磷的回收率分别为97.2%～101.3%,97.8%～100.4%和97.3%～102.3%。所建立的分析方法可用于海水、河口水悬浮颗粒物及沉积物中不同形态磷的测定。     

The nutrient and trace metal geochemistry of a dredge plume

Field sampling of the dissolved and particulate material field downstream of a large volume bucket dredge operating in the lower Thames River estuary near New London, Connecticut, was conducted in order to examine the magnitude and character of the dredge-induced resuspension. These data indicate that large amounts of dissolved phosphate, ammonia, silica, manganese, copper and particulate materials are released into the water column, whereas cadmium concentrations were unaffected. Concentrations in the vicinity of the dredge exceed background levels by two to nine times for the dissolved materials and by two orders of magnitude for particulates. During the ebb cycle, downstream material concentrations decrease rapidly to background within approximately 180 m for dissolved materials and 700 m for particulates.Two mechanisms were found to control the distribution of materials downstream of the dredge: (a) physical transport, including advection, turbulent mixing and diffusion, and (b) geochemical processes (i.e. adsorption, desorption, precipitation, dissolution, etc.). The concentration of dissolved materials downstream of the dredge decrease at a first order exponential rate. The downstream distribution of the dissolved ammonia and silica was found to be consistent with the reactivity experiments (Figure 8) which predicted that PO₄ would undergo a decay in concentration in the presence of suspended sediments. Absorption of phosphate onto suspended sediments and gravitational settling of the suspended particulates were the processes. Manganese and copper underwent a dual transformation which involved an initial dissolution, followed by flocculation and possible coprecipitation as MnO₂. Cadmium concentrations in the water column were unaffected by the dredging process due to low pore water concentrations.The observed spatial distribution indicates that dredge-induced injection of dissolved and particulate materials is primarily a near field phenomenon producing relatively minor variations as compared to those caused by naturally occurring storm events. These latter systems have been shown (Tramontano, 1978; Bohlen et al., 1979) to produce estuary-wide variations in suspended materials, PO₄ and NH₄ concentrations increasing the mass of materials in suspension by at least a factor of two. This increase in total suspended load, PO₄ and NH₄, is nearly an order of magnitude larger than that produced by the dredge.     

Mercury fluxes between an impacted coastal lagoon and the Atlantic Ocean

The objective was to estimate the seasonal and inter-tidal variability of dissolved and particulate mercury fluxes between the Ria de Aveiro (Portugal) and the Atlantic Ocean. The mercury fluxes were estimated by means of a two-dimensional vertically integrated hydrodynamic model. Results showed that the particulate fraction plays an important role in the transport of mercury while the contribution of the seston fraction to the transport of mercury was always <0.5%. During spring tides, in summer, about 2% of mercury transported in seston was present in an organic form. The mass balance for the mercury fractions revealed that the mercury export to the Atlantic Ocean varied with season and tidal regime, mainly in terms of the relative importance of the dissolved and particulate fractions. An approximate range of values for the annual mass balance between 42 and 77 kg shows that the export of dissolved and particulate mercury makes little impact on the near shore region of the Atlantic Ocean and that the recovery of the lagoon from mercury contamination is likely to remain a long-term issue.     

Sample treatment with focused ultrasound and bath sonication as a powerful tool for the evaluation of cadmium pollution in estuarine waters

A new sample treatment was developed for the determination of dissolved cadmium in Tagus estuarine waters, based on focused ultrasound in conjunction with small volumes in the extraction steps for Cd pre-concentration. Cadmium was first pre-concentrated using a classical approach (APDC as the complexing agent and MIBK as the organic phase) and then back-extracted into HNO₃ with the aid of focused ultrasound, which reduced the acid concentration by more than one order of magnitude (from 4 to 0.1 mol L^− 3). This sample treatment was accomplished in less than 5 min, using low sample volume (20 mL), and low-volume, low-concentration reagents. The pre-concentration factor used in this work was 25, but different sample/organic volume ratios may be used in order to increase that value. The limit of detection and the limit of quantification in Tagus water samples were 0.03 nmol L^− 1 and 0.1 nmol L^− 3, respectively. Recoveries from spiked Tagus water were higher than 90%. The procedure was validated using the reference estuarine water NRC-SLEW-3. In the solubilization of Cd particulate, bath ultrasonication was used in conjunction with HNO₃ + HCl, followed by H₂O₂, which took about 2 instead of the usual 12 h (cooling included) when high-pressure microwave digestion is used.     

The distribution of Mn,Fe, Zn,Cd and Cu in Baltic seawater; a study on the basis of one anchor station

A total of 150 samples were collected at a 10-days' anchor station in the Bornholm basin (55° 31.1′N, 15° 32.1′E) and analyzed for dissolved (< 0.4 μm) and particulate trace metals. For dissolved Mn, large gradients have been found in the vertical distribution with minimum concentrations (< 0.2 μgl^?1) in the halocline zone and considerably higher values in the deep waters (up to 50 μgl^?1). Ultrafiltration studies indicate that dissolved Mn is probably present as Mn²⁺ in the oxygenated bottom layer. The primary production process was not evident in the particulate Mn profile; the suspended particulate material (SPM), however, shows a considerable enrichment with depth, apparently due to Mn-oxide precipitation.The distribution of dissolved Fe was rather homogeneous, with average concentrations throughout the water column between 0.86 and 1.1 μgl^?1, indicating that the oxidation of Fe²⁺ ions released from the sediments must already be complete in the very near oxidation boundary layer. Relatively high concentrations of particulate Fe were actually measured in the bottom layer, with the maximum mean of 11.2 μgl^?1 at 72 m. Similarly to Mn, the profile of particulate Fe does not reflect the SPM curve of the eutrophic layer. On average, about 70% of the total Fe in surface waters was found to be particulate.The average concentrations of dissolved Zn, Cd and Cu were found to be rather homogeneous in the water column but showed a relatively high variability with time. A simplified model on trace-metal uptake by phytoplankton indicates no significant change in dissolved metal concentrations during the period of investigation. On average, only 1.7% Zn, 3.3% Cd and 9.8% Cu of the total metal concentrations were found in particulate form. SPM analyses showed significant correlations of Zn, Cd and Cu with Fe, indicating that particulate iron is an important carrier for particulate trace metals in Baltic waters.     

Metal distributions and their fluxes at the coastal boundary of a semi-enclosed ria

Water column samples have been collected in the outer channel of the Ferrol Ria (NW Spain) during four occasions over a tidal cycle. The objective was to study the exchange of dissolved and particulate Cd, Cu, Pb and Zn and particulate Al, Fe and Si between the ria and the adjacent coastal waters. This study provides the first extensive dataset on dissolved and particulate metal concentrations in the water column of a Galician ria. Typical concentrations of dissolved Cd (96 ± 31 pM), Cu (8 ± 4 nM), Pb (270 ± 170 pM) and Zn (21 ± 10 nM) were similar than in other European Atlantic shelf and coastal waters. The fraction of metals in the particulate phase followed the trend: Pb > Cu Zn > Cd. The outgoing water from the ria was enriched in dissolved and particulate Cu, Pb and Zn compared with incoming waters, whereas Cd concentrations were similar for both waters. The suspended particulate matter was composed of a mixture of marine and continental material. The latter end-member was found to arise from the metal-rich ria bed sediments, which is diluted by the dominant metal-poor marine end-member. The net output flux of Cu from the channel is balanced by the freshwater inputs to the ria, and the net Zn flux gave a positive output to coastal waters. For Pb, the net flux to the coastal waters is less than that input from the rivers, as a result of its particle reactivity and deposition in sediments. On the contrary, a net input flux of dissolved Cd from coastal waters was observed, highlighting the oceanic source of this metal in the Galician rias. Results from the budget calculations are in agreement with the differential geochemical behavior of these elements in coastal waters.     

The behavior of iron,manganese and silicon in the Peconic River estuary,New York

The behavior of dissolved and particulate iron and manganese and dissolved silicon has been studied as a function of chlorinity in the Peconic River estuary, New York. This study sought to identify important geochemical processes in a relatively pristine estuary facing increasing anthropogenic impact.Dissolved iron behaved in the classical non-conservative manner exhibiting removal of nearly 80% at very low chlorinities, while particulate iron increased by a corresponding amount over the same chlorinity range. Dissolved manganese was enriched by up to 200% over its predicted concentration at low and intermediate chlorinities by desorption from suspended particulates and by a probable benthic flux. Dissolved silicon was enriched by up to 100% at low and intermediate chlorinities also from a probable benthic flux. These fluxes were estimated to be 5 μg cm^?2 day^?1 for dissolved manganese and 70 μg cm^?2 day^?1 for dissolved silicon.The quantity of both particulate iron and manganese increased at high chlorinities due to an influx of suspended inorganic particulates. In the intermediate to high chlorinity region, oxidation of sediment-derived manganese is believed to contribute to the observed increase in particulate manganese.Total iron was essentially conservative throughout most of the estuary, while total manganese was non-conservative presumably due to extensive remobilization of dissolved manganese from the sediments.     

Temporal and spatial distribution of dissolved copper, lead, zinc and cadmium in the Changjiang Estuary and its adjacent waters

Heavy metal concentrations were measured in the Changjiang Estuary and its adjacent waters. Results from a systematic survey in April 2002 to March 2003 indicate that the ranges of the concentrations of dissolved copper, lead, zinc and cadmium in the study waters are 1.01 - 6.86, 0. 10 - 0.39,3.17 - 9.12 and 0.011 - 0. 049 μg/dm^3 , respectively. Similar to zinc, the behavior of dissolved copper was essentially conservative, but high scatter has been observed for high salinity samples, which can be attributed to the decomposition or mineralization of organic matter by bacteria. Dissolved lead may have active behavior with an addition at high salinity. Overall concentrations of dissolved cadmium increase with salinity. The mean values of these dissolved metals calculated for the surface waters were higher than those for the middle and bottom ones. External inputs of dissolved heavy metals to the surface waters were the likely explanation for these higher values. The maximum seasonal average values of dissolved copper and zinc were found in summer, reflecting higher amounts of riverine input in this season. In contrast, the maximum seasonal average values of dissolved lead and copper were found in winter and the lowest ones in summer, respectively, which might be asso- ciated with a combination of low concentration with heterogeneous scavenging. Concentrations of these dissolved metals found for the Changjiang Estuary fall in the range observed for the other estuaries but are noticeably higher than those from uncontaminated rivers, except for cadmium. Compared with observations for the Changjiang Estuary in the last two decades, it is clear that the Changjiang estuarine waters has been contaminated with copper, lead, zinc and cadmium during China＇ s industrialization, but concentrations of them have decreased in the last few years.     

Cadmium-binding proteins in the blue crab, callinectes sapidus: laboratory-field comparison

The blue crab, Callinectes sapidus, is distributed along the east coast of the United States from Cape Cod, Mass., through the Gulf of Mexico, including both relatively unpolluted coastal areas and estuaries contaminated with trace metals. Cadmium is of particular concern because it is concentrated in the digestive glands of blue crabs and can be passed on to consumer organisms. Tissue concentrations and partitioning of trace metals from crabs exposed in the laboratory to 10 ppb dissolved cadmium for 40 days were compared with blue crabs collected from two locations on the Hudson River, NY, Foundry Cove and Haverstraw Bay, Foundry Cove and Haverstraw Bay, both of which have elevated trace metal levels relative to estuarine areas near Beaufort, NC. Crab digestive glands, gills and muscle were removed and analyzed for total cadmium, copper, zinc and nickel concentrations using acid digestion and atomic absorption spectrophotometry, and metal-binding (metallothionein-like) proteins were determined by gel-filtration chromatography. In crabs exposed to cadmium in the laboratory, the cytosolic partitioning was similar to previous investigations at our laboratory where higher levels of cadmium (100 ppb) and shorter exposure times (14 days) were used. The similarity in cadmium partitioning from these two separate experiments indicates dose independence. In crabs from polluted environments the digestive glands contained the highest concentrations of trace metals. Chromatograms of the cytosol from the digestive glands and gills from both field and laboratory exposed crabs showed similar distributions of cadmium, copper and zinc. The gills of both field and laboratory-exposed crabs had metal-binding proteins that contained mostly cadmium, and the digestive glands had metallothionein-like proteins that contained cadmium, copper and zinc. Estimated molecular weights for these proteins were similar to the metallothioneins found in other crustaceans and mammals.     

溶解有机碳在混合水中的行为研究

研究溶解有机碳(DOC)在海水和黄河水所组成的混合水中的迁移转化行为,结果表明,海水和已过滤黄河水混合时,DOC呈近似的保守性;海水与未过滤的黄河水混合时,DOC呈明显的非保守性。通过研究沉积物对DOC的解吸过程,发现沉积物在盐水中能解吸出DOC,随着盐度的增大,其解吸量也迅速增大。因此可以认为,DOC在河口区的非保守行为是DOC的絮凝和颗粒物的解吸共同作用的结果。     

Chemical and GC-MS characterization of marine particulate lipids

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

Vertical concentration gradients of heavy metals in cultured mussels

Cultured mussels, Perna canaliculus (Gmelin), from two widely separated locations in New Zealand have been analysed for variation in heavy metal content with depth. The mussels, which are grown on vertically suspended ropes to a depth of 9 m, have been analysed for cadmium, lead, iron, and zinc at 1‐m intervals. At the first location (Kenepuru Sound), cadmium, lead, and iron increased with depth, while zinc decreased with depth. At the second location (Waiheke Island), concentrations of the four metals all remained essentially constant with depth. The differences in vertical concentration gradients between these two locations must result from differences in mixing of the water column. The differences in mixing may cause variations in the type of food organisms with depth, or variations in the ratio of particulate v. dissolved metal levels with depth. Either or both of these conditions could result in differences in the bioavailability of these metals with depth.     

夏季辽河口各形态营养盐的河口混合行为

利用2009 年7 月对辽河口水域航次的调查结果, 对该水域营养盐的形态和分布特征进行了探讨,并对其主要控制过程进行了讨论。结果表明： 辽河口水域营养盐的变化范围较大。磷主要以磷酸盐的形式存在, 其余依次是颗粒态磷PP、溶解有机磷DOP, 三者含量相差不大; 氮主要以硝酸盐的形式存在, 其余依次是溶解有机氮DON、颗粒...     

The behaviour of dissolved silica during the mixing of river and sea waters in Tokyo Bay

The behaviour of dissolved silica was studied in Tokyo Bay during six surveys in 1979 and 1980. The data from late spring and mid-summer samples showed concave mixing curves of silica versus salinity, whereas for the winter samples a simple conservative dillution curve was obtained. Plots of particulate silicon to particulate aluminium showed that even for winter samples as well as summer ones there were some processes removing silica from solution. The processes could not be adequately explained by adsorption onto suspended solids. The data are indicative of uptake by diatoms as the principal removal mechanism. Most of the diatom skeletons settled to the bottom where dissolution was rapid. The silica-salinity curves in this study thus demonstrate an apparent removal process for dissolved silica. This is because during summer the displacement rate of biogenic silica from a unit water column to the bottom as fecal pellets or by sinking is greater than the supply rate of dissolved silica by the action of diffusion and mixing of bottom water enriched with dissolved silica whereas in winter these rates are reasonably balanced.     

Distributions of dissolved and particulate biogenic thiols in the subartic Pacific Ocean

Dissolved and particulate concentrations of the biogenic thiols cysteine (Cys), arginine–cysteine (Arg–Cys), glutamine–cysteine (Gln–Cys), γ-glutamate–cysteine (γ-Glu–Cys) and glutathione (GSH) were measured in the subartic Pacific Ocean in the summer of 2003 using high performance liquid chromatography (HPLC) with precolumn derivatization as reported in previous work. In this study, a preconcentration protocol for the derivatized thiols was utilized to extend detection limits of dissolved thiols to picomolar levels. The measured concentrations of particulate and dissolved thiols were uncoupled, with distinctive depth profiles and large differences in the particulate to dissolved ratios between individual compounds. Glutathione was the most abundant particulate thiol whereas the most abundant dissolved thiol was γ-Glu–Cys, with concentrations as high as 15 nM. Given the relatively small pool of intracellular γ-Glu–Cys and the very low dissolved concentrations of GSH, we hypothesize that glutathione released from cells is rapidly converted to the potentially degradation resistant γ-Glu–Cys outside the cell. The relatively high concentrations of other dissolved thiols compared to particulate concentrations implies both biological exudation and slow degradation rates. Some thiols appear to vary with changes in nutrient availability but this effect is difficult to decouple from changes in community structure inferred from pigment analyses. Dissolved thiol concentrations also exceed typical metal concentrations in the subartic Pacific, supporting previous arguments that they may be important in metal speciation.