Particle–water interactions of 2,2′,5,5′-tetrachlorobiphenyl under simulated estuarine conditions

A batch sorption technique for the determination of particle–water interactions of hydrophobic organic micropollutants under simulated estuarine conditions is described. Results are presented for the behaviour of 2,2′,5,5′-tetrachlorobiphenyl (2,2′,5,5′-TCB) in river and sea waters, both in the presence and absence of estuarine suspended particles. Adsorption onto particles in sea water was enhanced compared with adsorption in river water owing to salting out of the compound, and possibly of the particulate organic matter, in the presence of high concentrations of dissolved ions. The particle–water distribution coefficient, K_D, decreased from about 120×10³ to 10×10³ ml g⁻¹, and from about 150×10³ to 20×10³ ml g⁻¹, in river water and sea water, respectively, over a particle concentration range of 10–1000 mg l⁻¹. Incomplete recovery of compound from the reactor walls is partly responsible for a particle concentration effect, while artefacts relating to inadequate sediment and water phase separation were ruled out following further experiments. The particle concentration effect, which is replicated in many field studies of hydrophobic organic micropollutants, including 2,2′,5,5′-TCB, is incorporated into a simple partitioning model and is discussed in the context of the likely estuarine behaviour of such compounds.     

Diagenetic fate of organic contaminants on the Palos Verdes Shelf, California

Municipal wastes discharged through deepwater submarine outfalls since 1937 have contaminated sediments of the Palos Verdes Shelf. A site approximately 6–8 km downcurrent from the outfall system was chosen for a study of the diagenetic fate of organic contaminants in the waste-impacted sediments. Concentrations of three classes of hydrophobic organic contaminants (DDT+metabolites, polychlorinated biphenyls (PCBs), and the long-chain alkylbenzenes) were determined in sediment cores collected at the study site in 1981 and 1992. Differences between the composition of effluent from the major source of DDT (Montrose Chemical) and that found in sediments suggests that parent DDT was transformed by hydrolytic dehydrochlorination during the earliest stages of diagenesis. As a result, p,p′-DDE is the dominant DDT metabolite found in shelf sediments, comprising 60–70% of ΣDDT. The p,p-DDE/p,p′-DDMU concentration ratio decreases with increasing sub-bottom depth in sediment cores, indicating that reductive dechlorination of p,p′-DDE is occurring. Approximately 9–23% of the DDE inventory in the sediments may have been converted to DDMU since DDT discharges began ca. 1953. At most, this is less than half of the decline in p,p′-DDE inventory that has been observed at the study site for the period 1981–1995. Most of the observed decrease is attributable to remobilization by processes such as sediment mixing coupled to resuspension, contaminant desorption, and current advection. Existing field data suggest that the in situ rate of DDE transformation is 10²–10³ times slower than rates determined in recent laboratory microcosm experiments (Quensen, J.F., Mueller, S.A., Jain, M.K., Tiedje, J.M., 1998. Reductive dechlorination of DDE to DDMU in marine sediment microcosms. Science, 280, 722–724.). This explains why the DDT composition (i.e. o,p′-, p,p′-isomers of DDE, DDD, DDT) of sediments from this site have not changed significantly since at least 1972. Congener-specific PCB compositions in shelf sediments are highly uniform and show no evidence of diagenetic transformation. Apparently, the agents/factors responsible for reductive dechlorination of DDE are not also effecting alteration of the PCBs. Two types of long-chain alkylbenzenes were found in the contaminated sediments. Comparison of chain length and isomer distributions of the linear alkylbenzenes in wastewater effluent and surficial sediment samples indicate that these compounds undergo biodegradation during sedimentation. Further degradation of the linear alkylbenzenes occurs after burial despite relatively invariant isomer compositions. The branched alkylbenzenes are much more persistent than the linear alkylbenzenes, presumably due to extensive branching of the alkyl side chain. Based on these results, p,p′-DDE, PCBs, and selected branched alkylbenzenes are sufficiently persistent for use in molecular stratigraphy. The linear alkylbenzenes may also provide information on depositional processes. However, their application as quantitative molecular tracers should be approached with caution.     

Transport and accumulation of organochlorines in the ovaries of Atlantic croaker (Micropogonias undulatus)

The role of vitellogenin in the transport of organochlorines was investigated in Atlantic croaker (Micropogonias undulatus) by exposing them through the diet to o,p′-DDT at a concentration of 10.8 μg/100 g fish/day for 14 days or Aroclor 1254 (PCB) at a concentration of 0.5 mg/100 g fish/day for 30 days during gonadal recrudescence. Tissue samples were taken from the fish at various times after initial exposure, and o,p′-DDT and PCBs were extracted in acetonitrile and analyzed by gas chromatography. Analysis of the ovarian tissue collected 2 and 3 weeks from the start of exposure revealed that the o,p′-DDT concentration increases as the gonadosomatic index (GSI) increases (r² = 0.63), with accumulation ranging from less than 1% to as much as 8% of the total dosage. Interestingly, o,p′-DDT did not accumulate in the testes during the same exposure period. Accumulation of PCBs was found to be 40 times higher in the ovaries than in the testes. Gel filtration of plasma from exposed females showed that o,p′-DDT elutes in the low density lipoprotein and vitellogenin fractions. Control plasma incubated with o,p′-DDT at 4 °C for 16 h followed by chromatography on Sepharose 6B gave similar results with an o,p′-DDT concentration of 0.6μg/mg protein in the vitellogenin fraction. Furthermore, both o,p′-DDT and PCBs were found to bind to purified croaker vitellogenin. These results suggest that lipoproteins, including vitellogenin, are involved in the transport and accumulation of organochlorines in the ovaries of exposed fish.     

The DNA de-methylating agent 5-azacytidine does not restore CYP1A induction in PCB resistant Newark Bay killifish (Fundulus heteroclitus)

Newark Bay (NB) killifish (Fundulus heteroclitus) have been chronically exposed to environmental contaminants that activate the aryl hydrocarbon receptor (AHR) and are tolerant to toxic effects and CYP1A induction provoked by AHR ligands. Resistance to CYP1A induction could be due to an epigenetic mechanism such as DNA methylation. We measured in-ovo CYP1A catalytic activity (ethoxyresorufin-O-deethylase, EROD) in NB and reference site killifish embryos aqueously exposed to various concentrations of the de-methylating agent 5-azacytidine, 5-AC (5, 50 and 500 μ(micro)M) with or without 0.2 μ(micro)g/l of the CYP1A inducer 3,3^′,4,4^′,5 pentachlorobiphenyl (IUPAC PCB126). Neither PCB126 alone, nor PCB126 plus 5-AC, induced EROD above levels in vehicle treated Newark Bay fish. In reference site fish, the same PCB126 dose provoked a 7.4-fold EROD induction relative to controls. We conclude that Newark Bay killifish are resistant to CYP1A induction by co-planar PCBs during early embryological development and our data suggests that DNA methylation does not play a critical role in resistance to CYP1A induction in this model.     

Effects of three fungicides alone and in combination on glutathione S-transferase activity (GST) and cytochrome P-450 (CYP 1A1) in the liver and gill of brown trout (Salmo trutta)

In order to evaluate the gill glutathione S-transferase (GST) activity as a biomarker of effect of fungicide exposure in juvenile brown trout (Salmo trutta), the fungicides propiconazole {(R,S)-1-[2-(2,4-diclophenyl)-4-propyl-1,3-dioolan-2-ylmetyl]-1H-1,2,4-triazole} and fenpropimorph {(±)-cis-4-[3-(4-tert-butylphenyl)-2-metyl propyl]-2,6 dimetylmorfolinc} were administrated in the water separately and together in a static system (80 μg/l for each pesticide) for 5 days. The combined fungicides gave a significant decrease in gill GST activity towards 1-chloro-2,4-dinitrobenzene (CDNB), whilst hepatic GST-activity was not significantly changed. Furthermore, continuous exposure to 540 ug/l thiabendazole{ 2-(thiazol-4′-yl)benzimidazole} in a flow-through system for 4 days significantly increased the gill glutathione S-transferase (GST) activity towards CDNB, whilst hepatic GST and cytochrome P450 (CYP 1A) activities were not increased by the treatment.     

Patterns in tropical seagrass photosynthesis in relation to light, depth and habitat

Seagrass meadows across north-eastern Australia, survive a range of environmental conditions in coastal bays, reefs, estuarine and deepwater habitats through adaptation of a range of structural, morphological and physiological features. The aim of this study was to investigate the influence of spatial features (habitat type, site and depth) and photon flux on the photosynthetic performance of 11 tropical seagrass species. Pulse amplitude modulated (PAM) fluorometry was used to generate rapid light curves from which measures of maximal electron transport rate (ETR_max), photosynthetic efficiency (α), saturating irradiance (E_k) and effective quantum yield (ΔF/F_m′) were derived. The amount of light absorbed by leaves (absorption factor) was also determined for each population. In intertidal habitats many seagrass species exhibited typical sun-type responses with a close coupling of both ETR_max and E_k with photon flux. Photosynthetic performance ranged from minima in Thalassodendron ciliatum to maxima in Syringodium isoetifolium. The absence of a coupling between photosynthetic performance and photon flux in subtidal populations was most likely due to highly variable light climates and possible light attenuation, and hence the photo-biology of estuarine and deepwater seagrasses exhibited photosynthetic responses indicative of light limitation. In contrast seagrass species from shallow reef and coastal habitats for the most part exhibited light saturation characteristics. Of all the variables examined ETR_max, E_k and ΔF/F_m′ were most responsive to changing light climates and provide reliable physiological indicators of real-time photosynthetic performance of tropical seagrasses under different light conditions.     

The solubility of CaCO3 in seawater at 2°C based upon in-situ sampled pore water composition

Analyses of the concentration product (Ca²⁺) × (CO₃²⁻) in the pore waters of marine sediments have been used to estimate the apparent solubility products of sedimentary calcite (K′_SPc) and aragonite (K′_SPa) in seawater. Regression of the data gives the relation In K′^P_SPc = 1.94 × 10⁻³ δP − 14.59 The 2°C, 1 atm value of K′_SPc is, then, 4.61 × 10⁻⁷ mol² l⁻². The pressure coefficient yields a at 2°C of −43.8 cm³ atm⁻¹. A single station where aragonite is present in the sediments gives a value of K′_SPa = 9.2 × 10⁻⁷ (4°C, 81 atm). The calcite data are very similar to those determined experimentally by Ingle et al. (1973) for K′_SPc at 2°C and 1 atm. The calculated is also indistinguishable from the experimental results of Ingle (1975) if is assumed to be independent of pressure.     

o,p′-DDT induction of vitellogenesis and its inhibition by tamoxifen in Nile tilapia (Oreochromis niloticus)

In order to investigate the mechanism by which o,p′-DDT disrupts endocrine functioning of Nile tilapia in vivo, the estrogenicity of o,p′-DDT was investigated in conjunction with 17β-estradiol (E₂) and tamoxifen. Mature, male tilapia were treated intraperitoneally with o,p′-DDT (60 mg/kg, one dose) or E₂ (5 mg/kg, four doses) in the presence or absence of tamoxifen (5 mg/kg, six doses) for 12 days and then plasma vitellogenin (Vtg) (measured as alkaline-labile phosphorous), E₂, and testosterone (T) were measured. Vtg levels were increased dramatically by E₂ (1744±171 μg/ml) and moderately by o,p′-DDT (82±15 μg/ml) compared with controls (23±3.5 μg/ml). Tamoxifen alone had no effect on Vtg production, but inhibited both E₂ and o,p′-DDT stimulated vitellogenesis. T levels were reduced with E₂ administration (1688±383 pg/ml) and declined further with the combined treatment of E₂ and tamoxifen (281±70 pg/ml), compared with controls (6558±1438 pg/ml). Tamoxifen or o,p′-DDT alone did not affect T levels, but their combined treatment did (2069±647 pg/ml). The results of this study suggest that o,p′-DDT is weakly estrogenic in male tilapia, and that this activity may be mediated through the estrogen receptor.     

Anomalously low alkenone temperatures caused by lateral particle and sediment transport in the Malvinas Current region, western Argentine Basin

We analysed the alkenone unsaturation ratio (U^K′₃₇) in 87 surface sediment samples from the western South Atlantic (5°N–50°S) in order to evaluate its applicability as a paleotemperature tool for this part of the ocean. The measured U^K′₃₇ ratios were converted into temperature using the global core-top calibration of Müller et al. (1998) and compared with annual mean atlas sea-surface temperatures (SSTs) of overlying surface waters. The results reveal a close correspondence (<1.5°C) between atlas and alkenone temperatures for the Western Tropical Atlantic and the Brazil Current region north of 32°S, but deviating low alkenone temperatures by −2° to −6°C are found in the regions of the Brazil–Malvinas Confluence (35–39°S) and the Malvinas Current (41–48°S). From the oceanographic evidence these low U^K′₃₇ values cannot be explained by preferential alkenone production below the mixed layer or during the cold season. Higher nutrient availability and algal growth rates are also unlikely causes. Instead, our results imply that lateral displacement of suspended particles and sediments, caused by strong surface and bottom currents, benthic storms, and downslope processes is responsible for the deviating U^K′₃₇ temperatures. In this way, particles and sediments carrying a cold water U^K′₃₇ signal of coastal or southern origin are transported northward and offshore into areas with warmer surface waters. In the northern Argentine Basin the depth between displaced and unaffected sediments appears to coincide with the boundary between the northward flowing Lower Circumpolar Deep Water (LCDW) and the southward flowing North Atlantic Deep Water (NADW) at about 4000 m.     

Solubility of calcite in the ocean

The apparent solubility product K′_sp of calcite in seawater was measured as a function of temperature, salinity, and pressure using potentiometric saturometry techniques. The temperature effect was hardly discernible experimentally. The value of K′_sp at 25°C was 4.59·10⁻⁷ mole²/(kg seawater)² at 35‰S, 5.34·10⁻⁷ at 43‰S, and 3.24·10⁻⁷ at 27‰S. The apparent partial molal volume was found to be −34.4 cm³ at 25°C and −42.3 cm³ at 2°C from a linear fit of log(K′_sp ^P/K′_sp ¹). These results were used in conjunction with field data to calculate the degree of saturation in the oceans and showed undersaturation at shallower depths than previously reported.     

Probabilistic model for wave forces acting on a cylinder in random waves

Generally, the sea-state (random waves) is best described by a wave spectrum. A number of statistical models for wave spectra has been well established and a sea-state can be specified. Once the specified sea-state is established, the corresponding model for wave forces acting on a single cylinder or a group of cylinders can be formulated. Since peak force is of more practical value, a multivariate or joint probability density function for wave forces has been developed for the peak force distribution of wave forces. This theoretical force model derives the tri-variate probability density function P(F, F′, F″), where F is the peak force defined by Morison equation. This model is of wide-band in nature and is tested by wave flume experiments.     

Apparent copper complexation capacity and conditional stability constants in north atlantic waters

Surface water samples were collected in the north Atlantic Ocean in July–August 1983. Their apparent complexation capacity for copper (CC_Cu) was determined on board, using differential pulse anodic stripping voltammetry under clean room conditions. Measurements were carried out by direct titrations as well as after equilibration of copper spikes. CC_Cu and conditional stability constants (K′) were calculated, by means of three different methods, which are compared.On the basis of salinity, temperature, silicate and phosphate concentrations the following surface waters could be distinguished: North Atlantic Drift (I), East Greenland Current (II), Labrador Current (III) and Gulf Stream waters (IV, V). CC_Cu and K′ were found to differ between these waters. The range of values for CC_Cu and their mean values given in parentheses, as calculated from van den Berg plots for waters I–IV are: I, 53–65 (59); II, 47–66 (55); III, 37–53 (45); IV, 20–42 (33) nM Cu. The range and mean values for log K′ are: I, 8.23–8.33 (8.28); II, 7.89–8.11 (7.98); III, 8.40–8.41 (8.41); IV, 7.90–8.21 (8.06).Information on complexation kinetics extracted from the titration curve revealed that k_f^′ is area-specific. The complexation rate constant in the northern part (Area I) is about two times larger than that in the southern area IV, (3.6 ± 0.3) and (2.2 ± 0.2) × 10⁴s⁻¹M⁻¹ Cu, respectively.Preliminary results for deep water samples suggest smaller but still existent CC_Cu and higher K′ than those found for surface waters.     

Complexation of calcium and copper with carbohydrates: Implications for seawater speciation

The extent of complexation of calcium(II) and copper(II) with 33 carbohydrates found in seawater has been determined potentiometrically using calcium and copper ion-selective electrodes. The measurements were performed in an essentially neutral aqueous medium at 25°C in 0.70 M KNO₃.Neutral sugars form very weak 1:1 complexes with Ca(II) and Cu(II) ions. Sugars with carboxylate groups from much stronger complexes. K′_Cu(II) >K′_Ca(II)) for a given sugar. The extent of complexation is dependent on the conformation of the sugar ligand.     

Glucuronidation in the polar bear (Ursus maritimus)

Polar bears bioaccumulate lipophilic pollutants, including polychlorinated biphenyls (PCBs), into their bodies from their exclusive diet of marine organisms. Hydroxylated PCB metabolites (OH-PCBs) have been found in plasma, presumably due to CYP-dependent biotransformation of PCBs in liver. Little is known about the phase 2 metabolism of hydroxylated xenobiotics in polar bears. The objective of this study was to examine UDP-glucuronosyltransferase (UGT) activity with OH-PCBs and a hydroxylated polycyclic aromatic hydrocarbon, 3-hydroxy-benzo(a)pyrene (3-OH-BaP), in polar bear liver. Samples of frozen polar bear liver were used to prepare microsomes. UGT activity with 3-OH-BaP in Brij-treated microsomes, measured by a fluorescence assay, was readily measurable with protein concentrations in assay tubes of up to 10 μg/ml, but dropped off very sharply at higher protein concentrations. The apparent K_m for 3-OH-BaP was 1.71 ± 0.04 μM, and V_max 1.26 ± 0.16 nmol/min/mg protein (mean ± SD, n=3). UGT activities with a model tetrachloro-OH-PCB (4^′-OH-CB72) and a model hexachloro-OH-PCB (4^′-OH-CB159) were assayed with [¹⁴-C]-UDPGA and separation of the [¹⁴-C]-glucuronide by ion-pair extraction and thin-layer chromatography. [¹⁴-C]-glucuronide conjugates were readily formed by polar bear liver microsomes in the absence of added substrate, apparently from contaminants present in liver. This phenomenon was not observed using hepatic microsomes from laboratory-held catfish. Glucuronidation efficiency was much higher with 4^′-OH-CB72 (K_m 7.3 μM; V_max 1.55 nmol/min/mg) than 4^′-OH-CB159 (K_m 16.1 μM; V_max 0.46 nmol/min/mg). The identities of the aglycones present in polar bear liver are not known, but could include OH-PCBs or hydroxylated metabolites of other persistent organic pollutants. This study demonstrates that UGT with high activity for 3-OH-BaP and other substrates is present in polar bear liver.     

Estradiol-17β and o,p′-DDT stimulate gonadotropin release in Atlantic croaker

Xenobiotic estrogens have the potential to act at a variety of estrogen-responsive target tissues on the hypothalamic-pituitary-gonadal axis. However, to date most studies in fish have focused on stimulation of vitellogenin synthesis by the liver. In the present study the effects of the xenoestrogen o,p′-DDT and estradiol-17β on the neuroendocrine control of gonadotropin secretion were compared. Atlantic croaker (Micropogonias undulatus) were exposed to o,p′-DDT (0.02 and 0.1 μgg⁻¹ body weight day⁻¹) in the diet for 3 and 7 weeks during the gonadal recrudescence phase. The o,p′-DDT exposure elicited a significant increase in plasma gonadotropin levels after both 3 and 7 weeks of exposure. The stimulatory effect of o,p′-DDT on basal (spontaneous) gonadotropin release was accompanied by a slight increase in ovarian growth as evidenced by the increase in gonadosomatic index. It appears that the stimulation of gonadotropin release by o,p′-DDT during early-recrudescence phase results in enhanced ovarian growth. A comparable stimulatory effect was observed with estradiol-17β treatment during early- and late-recrudescence phases of the ovarian cycle using three injections on alternate days and slow release silastic implants (five days). The present study provides the first evidence for an estrogen-like action of o,p′-DDT on gonadotropin release in a teleost model.     

Water masses and currents of deep circulation southwest of the Shatsky Rise in the western North Pacific

We conducted full-depth hydrographic observations in the southwestern region of the Northwest Pacific Basin in September 2004 and November 2005. Deep-circulation currents crossed the observation line between the East Mariana Ridge and the Shatsky Rise, carrying Lower Circumpolar Deep Water westward in the lower deep layer (θ<1.2 °C) and Upper Circumpolar Deep Water (UCDW) and North Pacific Deep Water (NPDW) eastward in the upper deep layer (1.3–2.2 °C). In the lower deep layer at depths greater than approximately 3500 m, the eastern branch current of the deep circulation was located south of the Shatsky Rise at 30°24′–30°59′N with volume transport of 3.9 Sv (1 Sv=10⁶ m³ s⁻¹) in 2004 and at 30°06′–31°15′N with 1.6 Sv in 2005. The western branch current of the deep circulation was located north of the Ogasawara Plateau at 26°27′–27°03′N with almost 2.1 Sv in 2004 and at 26°27′–26°45′N with 2.7 Sv in 2005. Integrating past and present results, volume transport southwest of the Shatsky Rise is concluded to be a little less than 4 Sv for the eastern branch current and a little more than 2 Sv for the western branch current. In the upper deep layer at depths of approximately 2000–3500 m, UCDW and NPDW, characterized by high and low dissolved oxygen, respectively, were carried eastward at the observation line by the return flow of the deep circulation composing meridional overturning circulation. UCDW was confined between the East Mariana Ridge and the Ogasawara Plateau (22°03′–25°33′N) in 2004, whereas it extended to 26°45′N north of the Ogasawara Plateau in 2005. NPDW existed over the foot and slope of the Shatsky Rise from 29°48′N in 2004 and 30°06′N in 2005 to at least 32°30′N at the top of the Shatsky Rise. Volume transport of UCDW was estimated to be 4.6 Sv in 2004, whereas that of NPDW was 1.4 Sv in 2004 and 2.6 Sv in 2005, although the values for NPDW may be slightly underestimated, because they do not include the component north of the top of the Shatsky Rise. Volume transport of UCDW and NPDW southwest of the Shatsky Rise is concluded to be approximately 5 and 3 Sv, respectively. The pathways of UCDW and NPDW are new findings and suggest a correction for the past view of the deep circulation in the Pacific Ocean.     

Quantum yield for the photochemical production of dissolved inorganic carbon in seawater

The direct photooxidation of coloured dissolved organic matter (CDOM) to dissolved inorganic carbon (DIC) may provide a significant sink for organic carbon in the ocean. To calculate the rate of this reaction on a global scale, it is essential to know its quantum yield, or photochemical efficiency. We have determined quantum yield spectra, φ(λ), (moles DIC/mole photons absorbed) for 14 samples of seawater from environments ranging from a turbid, eutrophic bay to the Gulf Stream. The spectra vary among locations, but can be represented quite well by three pooled spectra for zones defined by location and salinity: inshore φ(λ)=e^{−(6.66+0.0285(λ−290))}; coastal φ(λ)=e^{−(6.36+0.0140(λ−290))}; and open ocean φ(λ)=e^{−(5.53+0.00914(λ−290))}. Production efficiency increases offshore, which suggests that the most highly absorbing and quickly faded terrestrial chromophores are not those directly responsible for DIC photoproduction.     

Spectrophotometric pH measurement in estuaries using thymol blue and m-cresol purple

The conditional acid dissociation constants (pK_a′) of two sulfonephthalein dyes, thymol blue (TB) and m-cresol purple (mCP), were assessed throughout the estuarine salinity range (0<S<40) using a tris/tris–HCl buffer and spectrophotometric measurement. The salinity dependence of the pK_a′ of both dyes was fitted to the equations (25 °C, total proton pH scale, mol kg soln⁻¹):

The estimated accuracy of pH measurements using these calculated pK_a′ values is considered to be comparable to that possible with careful use of a glass electrode (±0.01 pH unit) but spectrophotometric measurements in an estuary have the significant advantage that it is not necessary to calibrate an electrode at different salinities. pH was measured in an estuary over a tidal cycle with a precision of ±0.0005 pH unit at high (S>30) salinity, and ±0.002 pH unit at low (S<5) salinity. The pH increased rapidly in the lower salinity ranges (0<S<15) but less rapidly at higher salinities.     

Chemical speciation of copper and zinc in surface waters of the western Black Sea

The chemical speciation of Cu and Zn was investigated by voltammetric titration methods in the surface waters (10 m) of the western Black Sea during an Istanbul–Sevastopol cruise conducted in November 1998. Supporting parameters (temperature (T), salinity (S), pH, alkalinity (Alk), suspended particulate matter (SPM) and dissolved and particulate ²³⁴Th) were obtained in order to distinguish hydrographic features against involvement of the metals in biogeochemical processes. In the Turkish continental slope region, the cruise track intersected a narrow vein of colder water originating on the western shelf. The core of this cold water vein was characterised by a relatively low salinity, higher specific alkalinity and higher metal (especially Cu) and metal-binding ligand concentrations.A very large portion of Cu (93–99.8%) and Zn (82–97%) was organically complexed. The degree of complexation was highest in shelf waters and lowest in the central gyre. Titration data for Cu were modelled by two classes of organic binding ligands characterised by (C_L1=3–12 nM, log K₁′=13.1–13.9) and (C_L2=20–70 nM, log K₂′=9.4–11.2). These ligands occurred mainly in the ‘dissolved’ phase, as defined by 0.4-μm filtration. The stronger Cu-binding ligand seemed to be produced in situ in response to Cu concentration, whereas the weaker Cu-binding ligand appeared to be derived from terrestrial sources and/or reducing shelf sediments. Titration results for Zn were generally represented by one class of ligands (C_L1=8–23 nM, log K₁′=9.4–10.2), which were almost uniformly distributed between the ‘dissolved’ (78±8%) and the particulate phase (22±8%). The concentration of these strong Zn-binding ligands showed a very good correlation with SPM (r²=0.64), which improved when the dissolved ligands alone were considered (r²=0.78). It is hypothesised that these ligands were produced in situ by the bacterial breakdown of particulate organic matter.