Water toxicity and metal contamination assessment of a polluted river: the Upper Vistula River (Poland)

In aquatic systems, the bioavailability of an element to microorganisms is greatly influenced by its chemical speciation. The goal of this work was to assess metal toxicity to a green algae (Pseudokirchneriella subcapitata) and a bacterium (Vibrio fisheri) as a function of size fractionation and chemical speciation (using the program MINTEQA2) in contaminated water of the Upper Vistula River. Water samples were collected at 1 reference site, 4 polluted sites and one polluted site on the Vistula's main tributary, the Przemsza River. Toxicity measurements were performed on unfiltered samples and, total dissolved (<1.2 μm), and truly dissolved (<1 kDa) fractions. Trace metal (Cd, Co, Cr, Cu, Mn, Pb, Zn) concentrations were measured in these samples and also in the colloidal fraction (1 kDa–1.2 μm). At the reference site, the low metal concentrations were in agreement with the absence of measurable toxicity. In the polluted section of the river, free metal concentrations were largely below the potential toxic levels for bacteria, which was in agreement with the absence of toxicity. Although Zn²⁺ was at potentially toxic-level concentrations in total dissolved and truly dissolved fractions in the polluted riverine section, toxicity for algae was observed, only in truly dissolved fractions from two stations. The absence of toxicity in most samples was related to metal association with particles and with low molecular weight ligands as well as the presence of organic ligands (phenol). The reason for toxic effects in two ultrafiltered samples is not clear, but may be related to the elimination of the colloidal organic fraction and thus the eradication of its protective effect occurring in natural samples.     

Geochemistry of Suspended Particulate Matter (SPM) in the Murray-Darling River System: A Conceptual Isotopic/Geochemical Model for the Fractionation of Major, Trace and Rare Earth Elements

A conceptual isotopic/geochemical model is presented to explain the variation of major, trace and rare earth element (REE) geochemistry and Sr isotope systematics in suspended particulate matter (SPM) as a function of particle/colloid size. This conceptual model is an extension of a previous investigation of the origin of SPM in the Murray-Darling River system (MDRS) that utilised Sr isotope systematics to examine aspects of SPM (particle/colloid) origin, structure and mineralogy. The geochemical processes that give rise to the often coherent trends in major, trace and REE geochemistry and Sr isotopic signature as a function of particulate (<1 μm) and colloidal (>1 μm) size in the MDRS have been identified using an enhanced SPM size fractionation technique as a basis to not only obtain a broad range of particle/colloid size ranges, but also to provide sufficient material for subsequent geochemical and isotopic analysis. The conceptual isotopic/geochemical model proposed here contains three major components: (i) the differential weathering of micas and alkali (K-) feldspars to form the majority of the particulate (<1 μm) fractions (high 87Sr/86Sr ratio), which have a geochemical and Sr isotopic signature that closely resembles precursor mineralogies, (ii) the differential weathering of Na, Ca-feldspars (plagioclase) which decompose to form clay minerals in the colloidal (>1 μm) fractions (low 87Sr/86Sr ratio), with a range of geochemical signatures related to the relative proportions of inorganic and organic constituents, and (iii) the presence of natural organic matter as coatings on the particulate (<1 μm) and colloidal (>1 μm) matter and possibly as organo-colloids which exert an increasing influence in particular on bulk colloid geochemistry with decreasing colloid size. This conceptual isotopic/geochemical model also accounts for the distinct variation in major, trace and REE geochemistry and Sr isotopic systematics between the particulate (<1 μm) and colloidal (>1 μm) fractions, the variation being primarily a function of the distinctly different precursor mineralogies of the SPM fractions and geochemical fractionation during the weathering and transport. Additionally, this model explains a systematic fractionation of REE apparent within colloidal (>1 μm) fractions. Statisitcal (hierachical cluster) analysis of two particulate and three colloidal fractions from 23 samples from the MDRS is used as a basis to investigate geochemical and mineralogical associations within the particulate and colloidal size fractions and to provide additional supporting evidence for the conceptual isotopic/geochemical model. This revised version was published online in July 2006 with corrections to the Cover Date.     

Metal species in a Boreal river system affected by acid sulfate soils

The bioavailability of metals and their potential for environmental pollution depends not simply on total concentrations but on their chemical form. Consequently, knowledge of aqueous metal speciation is essential in investigating potential metal toxicity and mobility. Dissolved (<1 kDa), colloidal (1 kDa–0.45 μm) and particulate (>0.45 μm) size fractions of sulfate, organic C (OC) and 18 metals/metalloids were investigated in the extremely acidic Vörå River system in Western Finland, which is strongly affected by acid sulfate (AS) soils. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these acidic waters. The most important finding of this study is that the very large amounts of elements known to be released from AS soils (including Al, Ca, Cd, Co, Cu, Mg, Mn, Na, Ni, Si and U) occur and can prevail mainly in toxic forms throughout acidic river systems; as free ions and/or sulfate-complexes. This has serious effects on the biota and particularly dissolved Al can be expected to have acute effects on fish and other organisms. In the study area, only the relatively forested upstream area (higher pH and contents of OC) had significant amounts of a few bioavailable elements (including Al, Cu, Ni and U) due to complexation with the more abundantly occurring colloidal OC in the upstream area. It is, however, notable that some of the colloidal/particulate metals were most likely associated with metal bearing phyllosilicates eroded from clay soils. Moreover, the mobilisation of Fe and As was small and As was predicted to be associated with Fe oxides, indicating a considerable influence of Fe oxides on the mobilisation/immobilisation processes of As. Elements will ultimately be precipitated in the recipient estuary, where the acidic metal-rich river water will gradually be diluted/neutralised with brackish seawater in the Gulf of Bothnia. According to speciation modelling, such a pH rise may first cause precipitation of Al, Cu and U together with organic matters closest to the river mouth, in line with previous sediment studies from the estuary.     

Metal speciation in rivers affected by enhanced soil erosion and acidity

Dissolved (<1 kDa), colloidal (1 kDa–0.45 μm) and particulate (>0.45 μm) size fractions of 30 elements were determined for four rivers (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), including 12 low-order inflow streams, largely affected by soil erosion and acidity in SW Finland. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these rivers. Total metal concentrations were relatively high but most of the elements occurred mainly in a colloidal or particulate form and even elements expected to be very soluble occurred to a large extent in colloidal form. According to geochemical modelling these patterns could be explained by in-stream metal complexation/adsorption only to a limited extent. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of acid sulphate (AS) soils, known to exist in the catchment, could be clearly distinguished in Sirppujoki river as it had very high concentrations of dissolved metals, while in the two nearby rivers (Laajoki and Mynäjoki) the influence of AS soils was largely masked by eroded phyllosilicates. In Paimionjoki river the colloidal and particulate fractions dominated very strongly, indicating that total metal concentrations are almost solely controlled by erosion of phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high “background” metal concentrations due to erosion of relatively non-toxic colloidal/particulate phyllosilicates. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring and/or speciation modelling can lead to a great overestimation of the water toxicity in this environment.     

Evaluation of the anthropogenic influx of metallic pollutants into Puck Bay,southern Baltic

Distributions of 15 elements with depth in two sediment cores from Puck Bay in the Gulf of Gdansk show that Ag, Cd, Pb, Zn and possibly Cu and Ni are anthropogenically enriched in the sediments there. The concentrations of these elements decrease sharply with depth in the sediment column and the elements are preferentially enriched in the <2 μm size fraction of the sediment. The sequence of element enrichment depends on whether the enrichment factor (EF) and the anthropogenic factor (AF) are used to calculate the element enrichment. By contrast, the anthropogenic elements show no systematic decrease in concentration with depth in a sediment core taken from near the mouth of the Vistula River. This reflects the higher sedimentation rate there such that the entire upper 20 cm of the core was deposited during the major, post-war period of industrialization in Poland. In addition, these elements are enriched in the 2–63 μm fraction compared to the <2 μm fraction in these sediments. This suggests that the heavy metals are mainly adsorbed on Fe oxyhydroxide particles with diameters greater than 2 μm at the hydrological front where Vistula river water mixes with brackish Baltic water. It appears that heavy-metal pollution of sediments in parts of Puck Bay may be greater than that near the mouth of the Vistula River which may reflect, in part, the higher sedimentation rate near the mouth of the Vistula River. The mode of incorporation of heavy-metals into the sediments in the two areas may also be different.     

Heavy metals in sediments as evidence for recent pollution and quasi-estuarine processes: an example from Lake Druzno,Poland

This article presents the results of a geochemical investigation of sediments from Lake Druzno (northern Poland), a reservoir fed by freshwater from the catchment, with periodic input of brackish water from Vistula Lagoon. This study analyzed the spatial variation in heavy metal content in surface sediments as well as the temporal changes in metal content in two sediment cores dated using the ²¹⁰Pb method. In the surface sediments, the highest metal concentrations were recorded in the northern part of the lake, with lower concentrations in the central and southern parts. Absolute values of metal concentrations in the cores were low, but normalization with respect to Al showed an increase during the second half of the 20th century. Mean enrichment factors (EF) in sediments from the second half of the 20th century ranged from insignificant (1–1.2) for Fe to (1.55–3.3) for Cu, Cd, Pb and Zn. The sediments deposited before 1950 had lower EF values (>1.5) and had low variability. Results from both the surface sediments and the cores indicate that the main source of lake pollution is brackish water intrusion from the Vistula Lagoon via the contaminated River Elbląg.     

The influence of channel morphology on the chemical partitioning of Pb and Zn in contaminated river sediments

The chemical partitioning of Pb and Zn was investigated in contaminated stream sediments from the River Ystwyth in mid-Wales, with changes in metal/substrate fixation being related to variations in channel morphology. Confinement of the channel by bedrock (chute zones) is sufficient to create very turbulent flow conditions facilitating the precipitation of Mn(IV) on surfaces of sand sized particles (2000-63 μm). Phase specific extraction of Pb (easily reducible fraction) from this particle size range indicates significant adsorption on precipitated forms of Mn. Conversely, under meandering conditions, association with the moderately reducible fraction (Fe-oxides) was more influential in the physico-chemical partitioning of Pb. Thus oxyhydroxide “precipitation zones” are created which affect heavy metal partitioning. These phenomena are, however, not observed on silt and clay sized particle coatings (<63 μm). The partitioning of Zn is not influenced by channel morphology due to a combined influence of the greater solubility of ionic species and subsequent transfer in solution and to the prevalence of total sediment Zn as sphalerite (ZnS).     

New operational method of testing colloid complexation with metals in natural waters

A dialysis procedure was used to assess the distribution coefficients of ∼50 major and trace elements (TEs) between colloidal (1 kDa–0.22 μm) and truly dissolved (<1 kDa) phases in Fe- and organic-rich boreal surface waters. These measurements allowed quantification of both TE partitioning coefficients and the proportion of colloidal forms as a function of solution pH (from 3 to 8). Two groups of elements can be distinguished according to their behaviour during dialysis: (i) elements which are strongly associated with colloids and exhibit significant increases of relative proportion of colloidal forms with pH increase (Al, Ba, Cd, Co, Cr, Cu, Fe, Ga, Hf, Mn, Ni, Pb, rare earth elements (REEs), Sr, Th, U, Y, Zn, Zr and dissolved organic C) and (ii) elements that are weakly associated with colloids and whose distribution coefficients between colloidal and truly dissolved phases are not significantly affected by solution pH (As, B, Ca, Cs, Ge, K, Li, Mg, Mo, Na, Nb, Rb, Sb, Si, Sn, Ti, V). Element speciation was assessed using the Visual MINTEQ computer code with an implemented NICA-Donnan humic ion binding model and database. The model reproduces quantitatively the pH-dependence of colloidal form proportion for alkaline-earth (Ba, Ca, Mg, Sr) and most divalent metals (Co, Cd, Mn, Ni, Pb, Zn) implying that the complexation of these metals with low molecular weight organic matter (<1 kDa fraction) is negligible. In contrast, model prediction of colloidal proportion (fraction of 1 kDa–0.22 μm) of Cu²⁺ and all trivalent and tetravalent metals is much higher than that measured in the experiment. This difference may be explained by (i) the presence of strong metal-binding organic ligands in the <1 kDa fraction whose stability constants are several orders of magnitude higher than those of colloidal humic and fulvic acids and/or (ii) coprecipitation of TE with Fe(Al) oxy(hydr)oxides in the colloidal fraction, whose dissolution and aggregation controls the pH-dependent pattern of TE partitioning. Quantitative modeling of metal – organic ligand complexation and empirical distribution coefficients corroborate the existence of two colloidal pools, formerly reported in boreal surface waters: “classic” fulvic or humic acids binding divalent transition metals and alkaline-earth elements and large-size organo-ferric colloids transporting insoluble trivalent and tetravalent elements.     

Geoecological investigations of the Ob-Irtysh River Basin in the Khanty-Mansi Autonomous region: Yugra in 2006–2007

This paper reports the results of the investigations of 2006–2007 on the distribution and migration forms of artificial radionuclides and chemical elements in the Ob-Irtysh water system. Three regions were studied. One of them is a local segment of the Ob River upstream from the confluence with the Irtysh River; its investigation allowed us to estimate the general radioecological state of the aquatic environment affected by the activity of the Tomsk 7 plant. The second region is a local segment of the Irtysh River upstream from its confluence with the Ob River, where the influence of emissions from the NPO Mayak could be estimated. The third region is the water area of the Ob River after its confluence with the Irtysh River. It characterizes the real level of radioactive and chemical contamination of the middle reaches of the Ob River.In order to explain horizontal variations in the distribution of radionuclides in the upper layer of bottom sediments collected at various sites, the results of sorption-kinetic experiments with radioactive tracers in the precipitate-solution system were used. The investigation of the migration forms of trace elements and radionuclides occurring in river water was based on the method of tangential-flow membrane filtration.Chemical element contents were determined in 400-ml water samples. A set of Millipore polysulfone membranes with pore sizes of 8, 1.2, 0.45, 0.1, and 0.025 μm was employed. Taking into account the ultralow specific concentrations of radionuclides in the water, they were analyzed in 300–500 litre samples using Millipore polysulfone membranes with pore sizes of 0.45 μm and 15 kDa. This allowed us to estimate the percentages of cesium-137 and plutonium-239, 240 in the suspended particulate fraction, colloids, and dissolved species.     

Beryllium-7 as a tracer to study mechanisms and rates of metal scavenging from lake surface waters

The removal of Be-7 from lake surface waters (Lake Lugano, Switzerland/Italy) was studied from September 1995 to May 1996. During this period the atmospheric input and sedimentary flux of Be-7, as well as concentrations of dissolved (<10 kD), colloidal (10 kD–1 μm), and particulate (>1 μm) Be-7 in the epilimnion were measured. The separation of dissolved, colloidal, and particulate fractions of Be-7 was carried out using continuous flow centrifugation (CFC) and tangential flow filtration (TFF) techniques. Lacustrine colloids (log K_c ≈ 6) were shown to be much more efficient sorbents for Be-7 than the suspended particles (log K_p 4–5). Particle concentrations C_p ranged from 0.5 to 2 mg/L. The ratio of colloid (>10 kD) to particle concentration C_c/C_p was close to 0.09 during winter months when detrital inputs are dominant, but was higher (0.16) in summer and in spring after an algal bloom. The Be-7 data were used to estimate coagulation rates of colloids. The highest coagulation rates (λ_coag ≈ 0.4 d⁻¹) along with the lowest K_c (log K_c ≈ 5.2) were found after an algal bloom in spring.     

Chlor-alkali industrial contamination and riverine transport of mercury: Distribution and partitioning of mercury between water,suspended matter,and bottom sediment of the Thur River,France

Total dissolved and total particulate Hg mass balances were estimated during one hydrological period (July 2001–June 2002) in the Thur River basin, which is heavily polluted by chlor-alkali industrial activity. The seasonal variations of the Hg dynamics in the aquatic environment were assessed using total Hg concentrations in bottom sediment and suspended matter, and total and reactive dissolved Hg concentrations in the water. The impact of the chlor-alkali plant (CAP) remains the largest concern for Hg contamination of this river system. Upstream from the CAP, the Hg partitioning between dissolved and particulate phases was principally controlled by the dissolved fraction due to snow melting during spring high flow, while during low flow, Hg was primarily adsorbed onto particulates. Downstream from the CAP, the Hg partitioning is controlled by the concentration of dissolved organic and inorganic ligands and by the total suspended sediment (TSS) concentrations. Nevertheless, the particulate fluxes were five times higher than the dissolved ones. Most of the total annual flux of Hg supplied by the CAP to the river is transported to the outlet of the catchment (total Hg flux: 70 μg m⁻² a⁻¹). Downstream from the CAP, the bottom sediment, mainly composed of coarse sediment (>63 μm) and depleted in organic matter, has a weak capacity to trap Hg in the river channel and the stock of Hg is low (4 mg m⁻²) showing that the residence time of Hg in this river is short.     

Solid–water partitioning of elements in Czech freshwaters

Partitioning of 41 elements between solids and water was studied by filtration and dialysis in situ in Czech freshwaters. Field-based distribution (partition) coefficients, K_D, between suspended particulate matter (SPM) and filtrate (‘dissolved’ fraction) differed by 4 orders of magnitude. The highest K_D values (log K_D>2.0 l/g) were exhibited by Zr, Al, Ce, Pb, La, Ti, Fe, Sm, Th and Cr which are extremely insoluble in near-neutral water or generally poorly soluble (Zr,Ti). The K_Ds decrease with element and DOC loading due to the relative increase of the element in the low molecular fraction. Log K_D mostly increased linearly with pH within a range from 3.5 to 9. K_D^U decreased at pH >6 due to carbonate complexation. The colloidal fraction (>1 kDa <0.4 μm) in a reservoir with a pH of 6.8 was mainly preferred by Fe, Pb, Be, Nb, Y, Al, Ni, U and Zr. When the colloidal fraction is not differentiated from true solution, then incorrect information about partitioning may be obtained and the highest K_D may decrease.     

Distribution of heavy metals and pollution pathways in a shallow marine shelf: assessment for a future management

The spatial distribution and geoaccumulation indices of four heavy metals were investigated in very shallow marine sediments of southwestern Spain. Surface sediments were collected from 43 sites with water depth ranging from 3 to 20 m. High to very high pollution levels (I _geo > 4 for zinc, lead and copper) were detected near the end of the Huelva bank, whereas chromium shows a more hazardous distribution in the southwestern Spanish littoral. Low to moderate heavy metal contents (mainly zinc and lead) were also observed in other two areas at different water depths (Isla Cristina-Piedras River: 10–18 m water depth; Mazagón–Matalascañas: <10 m water depth), whereas unpolluted to moderately polluted sediments were detected in the very shallow zones (<8 m water depth) located between the mouths of the Guadiana and the Piedras Rivers. A regional scenario indicates a strong pollution of the adjacent marine areas by polluted inputs derived from the Tinto–Odiel rivers, with a partial transport of heavy metals by W–E littoral currents even 40 km eastward. The Guadiana River is an additional source of zinc–lead contamination near the Spanish–Portuguese border, mainly at water depths up to 10 m. All these rivers are affected by acid mine drainage processes, derived from millennial mining activities. This pollution affects the sediment quality even 40 km eastward.     

Anthropogenic components of heavy metal (Cd,Zn, Cu,Pb) budgets in the Lot-Garonne fluvial system (France)

Heavy metal (Zn, Cd, Cu and Pb) mass balances in the Lot-Garonne fluvial system have been established for 1999 and 2000. The mean annual discharges of these years are close to the mean discharge of the previous decade. The estimated annual dissolved and particulate fluxes in this model watershed integrate daily input from diffuse and point sources, diffusive fluxes at the water/sediment interface, changes in the dissolved-particulate partition and changes in sediment stock. Cadmium, Zn, Cu and Pb entering the Gironde estuary via the Garonne River (11–14 t a⁻¹ of Cd; 1330–1450 t a⁻¹ of Zn; 126–214 t a⁻¹ of Cu and 127–155 t a⁻¹ of Pb) are mainly transported in the particulate phase and the major part (i.e. ∼74 to 96% for Cd, ∼60% for Zn, ∼50 to 60% for Cu and ∼80% for Pb) is transported by the Lot River. The main anthropogenic heavy metal point source is located in a small upstream watershed (Riou-Mort River) accounting for at least 47% (Cd), ∼20% (Zn), ∼4% (Cu) and ∼7 to 9% (Pb) of the total heavy metal inputs into the Garonne River, although it contributes only 1% of the discharge. Mass balances for 1999 suggest that under mean annual hydrologic conditions on the basin scale, the heavy metal budget of the Lot-Garonne fluvial system is balanced and that the stocks of Cd [200 t; Environ. Tech. 16 (1995) 1145] and Zn in the Lot River sediment are constant under mean discharge conditions. Heavy metal input by molecular diffusion at the sediment surface represents an important component of dissolved metal inputs into the system (e.g. 30% for Cu). Except for Cu, these dissolved inputs are totally removed from solution by SPM. Based on the generally constant Zn/Cd (∼50) concentration ratio in sediment cores from the polluted Lot River reaches and the sediment stock of Cd [200 t; Environ. Tech. 16 (1995) 1145], the present day Zn stock in the Lot River sediments has been estimated at about 10,000 t. In addition to the mobilization of river-bed sediment and associated heavy metals by intense floods, local human activities, including river-bed dredging, may strongly modify the heavy metal budget of the river system. In 2000, the dredging-related remobilization of polluted Lot River sediment released 2–6 t Cd. This additional Cd point source was estimated to account for 15–43% of the gross inputs into the Gironde Estuary.     

Sedimentary matter and organic compounds in the aerosols and surface waters along the Transatlantic section

Concentrations and composition of suspended particulate matter and organic compounds (OC), including Сorg, lipids, hydrocarbons (HC), and pigments, were determined in the near-water aerosol layer and in surface waters on the meridional section across the Atlantic Ocean from the port of Ushuaia to the port of Gdansk (Cruise 47^th of the R/V Akademic Ioffe, March 26–May, 7, 2015). It was established that the distribution of OC (except for pigments) in aerosols, in general, repeats the distribution of particle number and weight concentrations of aerosols, with maximums in the influence zone of fluxes from Patagonia and African deserts. The concentrations of aerosols changed within wide ranges: from 1237 to 111739 particles/L for 0.3–1 μm fraction; and from 0.02 to 19.890 μg/m³ for aerosols collected by network method (flux of 0.02–34.4 mg/m² day). The contrasting mineral composition of aeolian material reflects the diversity of its provenances. In surface waters, the studied compounds were accumulated in the frontal river–sea area (runoff of the Rio-Colorado River) and with approaching the coast, especially in the English Channel. A simultaneous change of concentrations of suspended particulate matter and OC is observed only in open oceanic waters.     

Distribution of colloidal trace metals in the San Francisco Bay estuary

The size distribution of trace metals (Al, Ag, Cd, Cu, Fe, Mn, Ni, Sr, and Zn) was examined in surface waters of the San Francisco Bay estuary. Water samples were collected in January 1994 across the whole salinity gradient and fractionated into total dissolved (<0.2 μm colloidal (10 KDa–0.2 μm) and < 10 kDa molecular weight phases. In the low salinity region of the estuary, concentrations of colloidal A1, Ag, and Fe accounted for ≥84% of the total dissolved fraction, and colloidal Cu and Mn accounted for 16–20% of the total. At high salinities, while colloidal Fe was still relatively high (40% of the dissolved), very little colloidal Al, Mn, and Cu (<10%) and no colloidal Ag was detectable. Colloidal Zn accounted for <3% of the total dissolved along the estuary, and colloidal Ni was only detectable (<2%) at the river endmember. All of the total dissolved Cd and Sr throughout the estuary consisted of relatively low molecular weight (<10 kDa) species. The relative affinity of metals for humic substances and their reactivity with particle surfaces appear to determine the amounts of metal associated with colloids. The mixing behavior of metals along the estuary appears to be determined by the relative contribution of the colloidal phase to the total dissolved pool. Metals with a small or undetectable colloidal fraction showed a nonconservative excess (Cd, Cu, Ni, and Mn) or conservative mixing (Sr) in the total dissolved fraction, relative to ideal dilution of river water and seawater along the estuary.

The salt-induced coagulation of colloidal A1, Fe, and Cu is indicated by their highly nonconservative removal along the salinity gradient. However, colloidal metals with low affinity for humic substances (Mn and Zn) showed conservative mixing behavior, indicating that some riverine colloids are not effectively aggregated during their transport to the sea. While colloidal metal concentrations correlated with dissolved organic carbon, they also covaried with colloidal Al, suggesting that colloids are a mixture of organic and inorganic components. Furthermore, the similarity between the colloidal metal:A1 ratios with the crustal ratios indicated that colloids could be the product of weathering processes or particle resuspension. Distribution coefficients for colloidal particles (K_c) and for large, filter-retained particles (K_d) were of the same magnitude, suggesting similar binding strength for the two types of particles. Also, the dependence of the distribution coefficients on the amount of suspended particulate matter (the so-called particle concentration effect) was still evident for the colloids-corrected distribution coefficient (K_p+c) and for metals (e.g., Ni) without affinity for colloidal particles.     

Composition of estuarine colloidal material: organic components

Colloidal material in the size range 1.2 nm to 0.4 μm was isolated by ultrafiltration from Chesapeake Bay and Patuxent River waters (U.S.A.). Temperature controlled, stepwise pyrolysis of the freeze-dried material, followed by gas chromatographic-mass spectrometric analyses of the volatile products indicates that the primary organic components of this polymer are carbohydrates and peptides. The major pyrolysis products at the 450°C step are acetic acid, furaldehydes, furoic acid, furanmethanol, diones and lactones characteristic of carbohydrate thermal decomposition. Pyrroles, pyridines, amides and indole (protein derivatives) become more prevalent and dominate the product yield at the 600°C pyrolysis step. Olefins and saturated hydrocarbons, originating from fatty acids, are present only in minor amounts. These results are consistent with the composition of Chesapeake phytoplankton (approximately 50% protein, 30% carbohydrate, 10% lipid and 10% nucleotides by dry weight). The pyrolysis of a cultured phytoplankton and natural particulate samples produced similar oxygen and nitrogencontaining compounds, although the proportions of some components differ relative to the colloidal fraction. There were no lignin derivatives indicative of terrestrial plant detritus in any of these samples. The data suggest that aquatic microorganisms, rather than terrestrial plants, are the dominant source of colloidal organic material in these river and estuarine surface waters.     

Concentrations and composition of aerosols and particulate matter in surface waters along the transatlantic section

Along the transatlantic section from Ushuaia to Gdańsk (March 26–May 7, 2015; cruise 47 of R/V Akademik Ioffe), data were obtained on the concentrations of aerosols in the near-water layer of the atmosphere and of particulate matter in surface waters, as well as of organic compounds within the considered matter (C_org, chlorophyll a, lipids, and hydrocarbons). The concentrations of aerosols amounted to 1237–111 739 particles/L for the fraction of 0.3–1 μm and to 0.02–34.4 μg/m²/day for the matter collected by means of the network procedure. The distribution of aerosols is affected by circumcontinental zoning and by the fluxes from arid areas of African deserts. The maximum concentration of the treated compounds were found in the river–sea frontal area (the runoff of the Colorado River, Argentina), as well as when nearing the coasts, especially in the English Channel.     

Distribution of polycyclic musks in water and particulate matter of the Lippe River (Germany)

The occurrence and distribution of polycyclic musks in the Lippe River system (a tributary of the Rhine River, Germany) was investigated in order to observe the dynamic transport and partitioning of these compounds between aqueous and particulate phases after their discharge into the river by sewage effluents. 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyrane (HHCB), 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), 6-acetyl-1,1,2,3,3,5-hexamethylindane (AHMI) and 4-acetyl-1,1-dimethyl-6-tert.-butylindane (ADBI) concentrations were determined in 19 water and surface sediment samples which were taken from a longitudinal section of the river. HHCB and AHTN were present in each of the water samples at concentrations ranging from <10 to 180 ng l⁻¹ and <10 to 70 ng l⁻¹, respectively. The load of dissolved HHCB and AHTN was calculated on the basis of compound concentrations in water and the corresponding river runoff data and ranged from 3 to 293 g day⁻¹ and from 1 to 108 g day⁻¹, respectively. Increasing loads of HHCB and AHTN along the river reflect a high input of sewage effluents to the densely populated areas along the central part of the river. Decreasing loads at the lower reaches indicate that in the corresponding river sections the rate of removal of musks was higher than the rate of input. Degradation and/or adsorption to particulate matter are processes that might explain this phenomenon. Consequently, high concentrations of HHCB and AHTN were detected in surface sediments from the Lippe River (from 5 to 191 μg kg⁻¹ and from 2 to 1399 μg kg⁻¹, respectively). HHCB/AHTN ratios in sediment samples were lower (average 1.2) than in water samples (average 2.9), suggesting the preferential adsorption of AHTN to particulate matter.