Copper speciation in estuarine waters by forward and reverse titrations

The chemical speciation of copper in the estuarine waters of the Vigo Ria was determined by titrations with salicylaldoxime (reverse copper titrations) and with copper (forward titrations). The forward titrations quantified the concentrations of ligands present in excess whereas the reverse titrations demonstrated the presence of low concentrations of very strong binding ligands, approximately matching the copper concentration. The data obtained by the reverse titrations indicated that copper was about 10× stronger bound than data based on the usual forward titrations.The copper concentration in these ria waters was low at 5 nM with a minor mid-estuarine maximum of 8 nM. These copper levels are amongst the lowest reported for estuarine waters and therefore represent uncontaminated waters. The concentration of inorganic copper was very low across the ria at  10–100 fM, except at Bouzas harbour (salinity 35.5) where it was raised to  1 pM due to copper contamination, in waters affected by the port facilities, to total levels of 15 to 20 nM copper, exceeding the concentration of the very strong ligand detected by the reverse titrations.     

Seasonal survey of copper-complexing ligands and thiol compounds in a heavily utilized, urban estuary: Elizabeth River, Virginia

Concentrations of thiol compounds, copper-complexing ligands, and total dissolved copper were followed over the course of 1 year (October 2002 until September 2003) in the Elizabeth River, Virginia to evaluate seasonality. Copper-complexing ligand concentrations were determined by competitive ligand equilibration-adsorptive cathodic stripping voltammetry (CLE/ACSV). Thiol detection was carried out by high performance liquid chromatography (HPLC) and calibration using a suite of nine thiol compounds (cysteine, glutathione, mercaptoacetic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, and monothioglycerol). Total dissolved copper concentrations reached a January low of 13.1 nM to a June high of 24.7 nM and were found to vary seasonally with higher concentrations occurring from June to September. With a low of 26 nM during April to a high of 56 nM in October, copper-complexing ligand (average log K′_CuL of 12.0 ± 0.2) concentrations displayed a similar seasonal pattern to that of total dissolved copper. Free cupric ion concentrations remained below 1.5 pM for a majority of the year except during March, April, and December when values reached pM levels greater than 1.5. Six of the nine thiol compounds surveyed were detected in the Elizabeth River samples and ranged in concentration from below detectable concentrations (< 5 nM) to individual highs ranging from 25.3 to168.5 nM. The thiol compound concentrations displayed a clear seasonality fluctuating at below detection limits during November to February then increasing with increasing surface water temperatures from March to July. CLE/ACSV was used to assess whether or not the suite of thiol compounds detected by HPLC could contribute to the copper-complexing ligand pool. Conditional stability constants for each one of six thiol standards (average log K′_CuL  12.1 ± 0.5) were found to be statistically equivalent to the naturally occurring copper-complexing ligands (average log K′_CuL  12.0 ± 0.2). This suggests that these thiol compounds could act as copper-complexing ligands in natural samples and could contribute to the copper-complexing ligand pool detected by CLE/ACSV. This study involving seasonality of copper-complexing ligands and thiols in an industrialized, urban estuary underscored several points that have to be substantiated in future research efforts including copper-complexing ligands sources and the role that thiol compounds as well as other unidentified organic compounds play in the copper-complexing ligand pool.     

Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.     

Mercury speciation in surface and deep waters of the Mediterranean Sea

Mercury speciation and its distribution in surface and deep waters of the Mediterranean Sea were studied during two oceanographic cruises on board the Italian research vessel URANIA in summer 2003 and spring 2004 as part of the Med Oceaneor and MERCYMS projects. The study included deep water profiles of dissolved gaseous Hg (DGM), reactive Hg (RHg), total Hg (THg), monomethyl Hg (MeHg) and dimethyl Hg (DMeHg) in open ocean waters. Average concentrations of measured Hg species were characterized by seasonal and spatial variations. Overall average THg concentrations ranged between 0.41 and 2.65 pM (1.32 ± 0.48 pM) and were comparable to those obtained in previous studies of the Mediterranean Sea. A significant fraction of Hg was present as “reactive” Hg (average 0.33 ± 0.32 pM). Dissolved gaseous Hg (DGM), which consists mainly of Hg⁰, represents a considerable proportion of THg (average 20%, 0.23 ± 0.11 pM). The portion of DGM typically increased towards the bottom, especially in areas with strong tectonic activity (Alboran Sea, Strait of Sicily, Tyrrhenian Sea), indicating its geotectonic origin. No dimethyl Hg was found in surface waters down to the depth of 40 m. Below this depth, its average concentration was 2.67 ± 2.9 fM. Dissolved fractions of total Hg and MeHg were measured in filtered water samples and were 0.68 ± 0.43 pM and 0.29 ± 0.17 pM for THg and MeHg respectively. The fraction of Hg as MeHg was in average 43%, which is relatively high compared to other ocean environments. The concentrations reported in this study are among the lowest found in marine environments and the quality of analytical methods are of key importance. Speciation of Hg in sea water is of crucial importance as THg concentrations alone do not give adequate data for understanding Hg sources and cycling in marine environments. For example, photoinduced transformations are important for the presence of reactive and elemental mercury in the surface layers, biologically mediated reactions are important for the production/degradation of MeHg and DGM in the photic zones of the water column, and the data for DGM in deep sea indicate the natural sources of Hg in geotectonicaly active areas of the Mediterranean Sea.     

Seasonal changes in speciation of dissolved chromium in the surface Sargasso Sea

The concentrations of Cr (III) and Cr (VI) were determined in the upper 500 m of the Sargasso Sea at different times of the year. Total Cr concentrations ranged between 2.5 and 4.5 nM, and the predominant species of Cr was the thermodynamically favoured Cr (VI). Cr (III) concentrations were greatest during periods of high biological activity, as indicated by strong correlations between the ratio of Cr (III):Cr (VI) and both bacterial biomass and primary productivity. Whilst the oxidation state varied substantially over the seasonal cycle, the upper water column inventory of Cr was relatively constant. The long residence time of Cr in the surface Sargasso Sea estimated with respect to atmospheric inputs (1410–2240 years) is indicative of the largely conservative behaviour of this element. Deep particle fluxes of Cr are similar or somewhat greater than atmospheric inputs, and this downward flux of Cr is well correlated with organic carbon fluxes from the upper Sargasso Sea. The long residence time coupled with the seasonal changes in oxidation state of Cr implies rapid seasonal recycling of Cr between redox states, with only slow removal via particles to the deep ocean at this site.     

黄东海表层沉积物中磷的赋存形态和分布特征及其对生态系统的潜在影响

For better understanding the phosphorus(P) cycle and its impacts on one of the most important fishing grounds and pressures on the marine ecosystem in the Yellow Sea(YS) and East China Sea(ECS), it is essential to distinguish the contents of different P speciation in sediments and have the knowledge of its distribution and bioavailability. In this study, the modified SEDEX procedure was employed to quantify the different forms of P in sediments. The contents of phosphorus fractions in surface sediments were 0.20–0.89 μmol/g for exchangeable-P(Exch-P), 0.37–2.86 μmol/g for Fe-bound P(Fe-P), 0.61–3.07 μmol/g for authigenic Ca-P(ACa-P), 6.39–13.73μmol/g for detrital-P(DAP) and 0.54–10.06 μmol/g for organic P(OP). The distribution of Exch-P, Fe-P and OP seemed to be similar. The concentrations of Exch-P, Fe-P and OP were slightly higher in the Yellow Sea than that in the East China Sea, and low concentrations could be observed in the middle part of the ECS and southwest off Cheju Island. The distribution of ACa-P was different from those of Exch-P, Fe-P and OP. DAP was the major fraction of sedimentary P in the research region. The sum of Exch-P, Fe-P and OP may be thought to be potentially bioavailable P in the research region. The percentage of bioavailable P in TP ranged from 13% to 61%. Bioavailable P burial flux that appeared regional differences was affected by sedimentation rates, porosity and bioavailable P content, and the distribution of bioavailable P burial flux were almost the same as that of TP burial flux.     

Zinc speciation in the Northeastern Atlantic Ocean

Measurements of zinc and zinc complexation by natural organic ligands in the northeastern part of the Atlantic Ocean were made using cathodic stripping voltammetry with ligand competition. Total zinc concentrations ranged from 0.3 nM in surface waters to 2 nM at 2000 m for open-ocean waters, whilst nearer the English coast, zinc concentrations reached 1.5 nM in the upper water column. In open-ocean waters zinc speciation was dominated by complexation to a natural organic ligand with conditional stability constant (log K_ZnL′) ranging between 10.0 and 10.5 and with ligand concentrations ranging between 0.4 and 2.5 nM. The ligand was found to be uniformly distributed throughout the water column even though zinc concentrations increased with depth. Organic ligand concentrations measured in this study are similar to those published for the North Pacific. However the log K_ZnL′ values for the North Atlantic are almost and order of magnitude lower than those reported by Bruland [Bruland, K.W., 1989. Complexation of zinc by natural organic-ligands in the central North Pacific. Limnol. Oceanogr., 34, 269–285.] using anodic stripping voltammetry for the North Pacific. Free zinc ion concentrations were low in open-ocean waters (6–20 pM) but are not low enough to limit growth of a typical oceanic species of phytoplankton.     

黄、东海海域溶解无解机砷分布特征与化学形态

Distribution and chemical speciation of dissolved inorganic arsenic were examined in Yellow Sea and East China Sea. Results demonstrated that: (1) both As(III) and As(V) were detected, with As(V) domin...     

Heavy metals in sinking particles and bottom sediments from the eastern Turkish coast of the Black Sea

Concentrations of Cd, Cu, Cr, Co, Ni, Zn, Fe, Mn, Pb, As, and Sb were determined in sediment trap and bottom sediment samples collected seasonally from a station on the eastern Turkish coast of the Black Sea. Cd, Pb and Mn concentrations were highest in the sediment trap samples except during the summer period, whereas Co, Ni, Zn and Fe levels were much lower than corresponding levels found in the surface sediments. Cu, Cr, As and Sb levels showed no definite trend with sediment type. In general, with the exception of Cr, relatively lower metal concentrations in the sediment trap material were determined in the summer period. The highest mass flux, 56.5 g m⁻² day⁻¹, was measured during autumn. The highest flux of heavy metals also occurred during autumn and was strongly dependent on particle mass flux. Based on these results, we suggest that the downward vertical transport of particulate heavy metals in this region is related to the high degree of land erosion and the resultant particulate flux dynamics, which occur here. It was noteworthy that the highest concentrations of Cd, Cu, Co, Zn, Fe and Sb in particles were measured during winter a finding which suggests that enhanced fossil fuel combustion, which occurs during this period in adjacent urban and industrial areas plays an important role in the metal composition of sinking particles in nearshore waters.     

南海表层水中的溶解态Cu,Pb, Zn,Cd

于1998年“南海海洋环境调查”外业工作期间在南海的各个站位,按照严格的防沾污措施采集了106个表层海水样品.采用溶剂萃取-石墨炉原子吸收法对样品中的痕量重金属Cu,Pb,Zn,Cd含量进行了分析测试.测得各重金属的平均值如下:Cu 0.100 μg/dm3,Pb 0.060μg/dm3,Zn 0.086 μg/dm3,Cd 0.007μg/dm3,接近世界大洋水的浓度水平.各重金属的空间分布呈现出海区周边含量高于中央,浓度有自近岸向远海逐渐减小的趋势.相关分析的结果表明各重金属夏季相关性优于冬季,Cu与Cd存在良好的正相关关系,并且首次在南海表层水发现Cu,Cd与营养盐的相关关系.将重金属浓度值作数理统计分析,得到它们在南海的基线值.     

Dissolved Cu, Pb, Zn and Cd in the South China Sea surface waters

The understanding of the distribution of trace heavy metals in the world ocean has greatlyimProved in the past decades. But most of the data are of vertical profiles of certain stations(Bruland, l980; Paul et al., l992; RObert et al., l990) and large--scale study of temporaland spatial variability of trace heaVy metals in the ocean is rather few. In fact, affected by ver-tical mixing by upwelling or convection, biogenic removal, atmospheric fallout and continentalinput frorn rivers, the dist…     

The performance of the Black Sea Commission as a collaborative governance regime

It is often claimed that the Black Sea is one of the most degraded seas in the world. Management to rehabilitate the Black Sea requires cooperation between the coastal countries to be successful. However, regional cooperation in the Black Sea is poorly coordinated and lack concrete outcomes. This article analyses the performance of the Black Sea Commission in terms of enabling and fostering effective regional collaboration between the Black Sea coastal countries. The results indicate that the measures undertaken by the Black Sea Commission are effective in terms of enabling scientific and project based cooperation between the Black Sea countries. The cooperation around regional and national institutional reforms to tackle the Black Sea environmental problems is found to be weak. Despite the existing mechanisms and willingness of countries to cooperate, the implementation of the established strategic action plan for the environmental protection and rehabilitation of the Black Sea is limited. Most of the limitations of the Black Sea Commission's regime are found in its institutional and legal frameworks, which constrain the effectiveness of collaborative efforts of the Black Sea countries. To be fully functional, the collaborative governance regime of the Black Sea Commission has to be improved. Recommendations as to how these may be addressed to enhance the regime's capacity to ensure effective marine collaborative governance in the region are presented in this article.     

Distribution and contamination of trace metals in surface sediments of the East China Sea

The distributions, contamination status and annual sedimentation flux of trace metals in surface sediments of the East China Sea (ECS) were studied. Higher concentrations of the studied metals were generally found in the inner shelf and the concentrations decreased seaward. The sequences of the enrichment factor (EF) of the studied metals are Cu > Mn > Ni > Zn > Pb > Fe. The values of EF suggest that the metals contamination in the middle and outer shelves of the ECS is still minor. The annual sedimentation fluxes of trace metals in the ECS were: Fe, 3.48 × 10⁷ t/y; Mn, 9.07 × 10⁵ t/y; Zn, 1.08 × 10⁵ t/y; Ni, 4.48 × 10⁴ t/y; Pb, 4.32 × 10⁴ t/y and Cu, 3.1 × 10⁴ t/y, respectively. Approximately 55–70% and 10–17% of the sedimentation fluxes of trace metals were deposited in the inner shelf and the Changjiang estuarine zone.     

Inputs of iron,manganese and aluminium to surface waters of the Northeast Atlantic Ocean and the European continental shelf

Dissolved Fe, Mn and Al concentrations (dFe, dMn and dAl hereafter) in surface waters and the water column of the Northeast Atlantic and the European continental shelf are reported. Following an episode of enhanced Saharan dust inputs over the Northeast Atlantic Ocean prior and during the cruise in March 1998, surface concentrations were enhanced up to 4 nmol L^− 1 dFe, 3 nmol L^− 1 dMn and 40 nmol L^− 1 dAl and returned to 0.6 nmol L^− 1 dFe, 0.5 nmol L^− 1 dMn and 10 nmol L^− 1 dAl towards the end of the cruise three weeks later. A simple steady state model (MADCOW, [Measures, C.I., Brown, E.T., 1996. Estimating dust input to the Atlantic Ocean using surface water aluminium concentrations. In: Guerzoni. S. and Chester. R. (Eds.), The impact of desert dust across the Mediterranean, Kluwer Academic Publishers, The Netherlands, pp. 301–311.]) was used which relies on surface ocean dAl as a proxy for atmospheric deposition of mineral dust. We estimated dust input at 1.8 g m^− 2 yr^− 1 (range 1.0–2.9 g m^− 2 yr^− 1) and fluxes of dFe, dMn and dAl were inferred. Mixed layer steady state residence times for dissolved metals were estimated at 1.3 yr for dFe (range 0.3–2.9 yr) and 1.9 yr for dMn (range 1.0–3.8 yr). The dFe residence time may have been overestimated and it is shown that 0.2–0.4 yr is probably more realistic. Using vertical dFe versus Apparent Oxygen Utilization (AOU) relationships as well as a biogeochemical two end member mixing model, regenerative Fe:C ratios were estimated respectively to be 20 ± 6 and 22 ± 5 μmol Fe:mol C. Combining the atmospheric flux of dFe to the upper water column with the latter Fe:C ratio, a ‘new iron’ supported primary productivity of only 15% (range 7%–56%) was deduced. This would imply that 85% (range 44–93%) of primary productivity could be supported by regenerated dFe. The open ocean surface data suggest that the continental shelf is probably not a major source of dissolved metals to the surface of the adjacent open ocean. Continental shelf concentrations of dMn, dFe, and to a lesser extent dAl, were well correlated with salinity and express mixing of a fresher continental end member with Atlantic Ocean water flowing onto the shelf. This means probably that diffusive benthic fluxes did not play a major role at the time of the cruise.     

Depositional environment and hydrocarbon source potential of the Oligocene Ruslar Formation (Kamchia Depression; Western Black Sea)

The Oligocene Ruslar Formation is a hydrocarbon source rock in the Kamchia Depression, located in the Western Black Sea area. Depositional environment and source potential of the predominantly pelitic rocks were investigated using core and cuttings samples from four offshore wells. In these wells the Ruslar Formation is up to 500 m thick. Based on lithology and well logs, the Ruslar Formation is subdivided from base to top into units I–VI. Dysoxic to anoxic conditions and mesohaline to euhaline salinities prevailed during deposition of the Ruslar Formation. Relatively high oxygen contents occurred during early Solenovian times (lower part of unit II), when brackish surface water favoured nannoplankton blooms and the deposition of bright marls (“Solenovian event”). Anoxic conditions with photic zone anoxia were established during late Oligocene times (units III and IV) and, probably, reflect a basin-wide anoxic event in the Eastern Paratethys during Kalmykian times. Organic carbon content in the Ruslar Formation is up to 3%. Autochthonous aquatic and allochthonous terrigenous biomass contribute to the organic matter. Relatively high amounts of aquatic organic matter occur in the lower part of the Ruslar Formation (units I and II) and in its upper part (unit VI). Diatoms are especially abundant in the lower part of unit VI. The kerogen is of type III and II with HI values ranging from 50 to 400 mgHC/gTOC. Units I and II (Pshekian, lower Solenovian) are characterized by a fair (to good) potential to produce gas and oil, but potential sources for gas and oil also occur in the Upper Oligocene units IV–VI.     

Further evidence of abrupt Holocene drowning of the Black Sea shelf

A 1999 survey of the Black Sea continental shelf off the north central Turkish seaport of Sinop using a side-scan sonar, small remotely operated vehicles, and a series of dredge lowerings located, inspected and sampled an exposed high-energy paleoshoreline at a depth of 155 m. Radiocarbon dating of mollusk shells collected from this ancient beach revealed that the marine flooding of the Black Sea took place between 7460 and 6820 yr B.P. (all ages are reported in radiocarbon years, not calendar years, without correction for reservoir age or dendro-calibration) changing it from a lacustrine to marine environment. This relic surface remained in contact with the bottom waters of the Black Sea for a long period of time before being draped by a thin layer of sapropel mud. Wood samples recovered from this same location were very well preserved and yielded dates as old as 3580 yr B.P.     

Validation of the WAMC4 wave model for the Black Sea

The present paper describes the set-up and application of the third-generation wave model — WAM Cycle 4 to the Black Sea. The wind fields are calculated by a regional atmosphere model (REMO), which was driven with the conditions from the global NCEP re-analysis project. These atmospheric data are used to force the state-of-the-art WAM model. The validation is done by comparison of wave model output against directional buoy measurements registered at three deep-water locations and wave gauge data taken at a point in intermediate depth near the Black Sea coast. The results reveal that agreement between modeled and measured data is satisfactory and the quality of the simulations increases under more energetic and severer wind and wave conditions. Following the validation, a 41-year wave hindcast was implemented spanning the period 1958–1998.     

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.     

Size distribution of colloidal trace metals and organic carbon during a coastal bloom in the Baltic Sea

The physico-chemical speciation of organic carbon and selected metals was measured during a coastal bloom in Ekhagen Bay, Baltic Sea, using ultrafiltration.One important objective with the study was to see if any depletion of trace metals could be measured in the directly bioavailable fraction (<1000 Da, the soluble low molecular weight fraction, LMW) during a plankton bloom. Filters with five different cut-offs were used (1 kD (1000 Da), 5 kD, 10 kD, 100 kD and 0.22 μm) in order to delineate the size distribution of colloidal organic carbon (COC) and trace metals.During the bloom in May, LMW Al, Co, Cu, Mn and Ni concentrations decreased although the colloidal and particulate concentrations were relatively high. Data show that desorption of colloidal and particulate bound trace metals to the LMW fraction was slower than the process depleting the LMW fraction.Estimates of the maximum active uptake of Cu, Ni and Mn by the phytoplankton, and the loss of non-bioactive Al from the LMW fraction, indicate that processes other than active uptake by phytoplankton must contribute to the observed depletion of trace metals in the LMW fraction. Hence, in order to estimate the bioavailable pool of trace metals for plankton during bloom conditions, these other processes must be understood and quantified.Transparent Exopolymeric Particles (TEP, reflecting sugar-rich phytoplankton exudates) increased around eight times during the plankton bloom. We hypothesize that the formation of TEP is a process that might be important for the transfer of trace metals from the LMW to the particulate fraction during the phytoplankton bloom, but the significance of TEP for this depletion in Baltic Sea surface water remains to be shown.