Spatial and temporal variation in particle size and particulate organic matter content in suspended particulate matter from peatland‐dominated catchments in Finland

Properties of suspended particulate matter play a vital role in transport processes, but information from boreal lowland river systems with high organic loads is limited. This study analysed data from 2 years of sampling at 30 locations in Finland (204 samples in total) using suspended particulate matter samplers to determine effective and absolute particle size and organic fractions. Mean d₅₀ value was 22 and 49 µm for absolute and effective particle size, respectively. The organic fraction content ranged from 2.1% to 36% (mean 9.6%), highlighting the importance of particle organic matter for suspended particulate matter flux in the region. The results indicated that the suspended particulate matter particle size distribution and load in the study region is dominated by composite particles. There were considerable spatial and temporal variations in transport of organic fractions, effective particle size and degree of aggregation (range 1.5–93%). Headwaters and, in particular, late summer and spring flood conditions with flow peaks produced the largest composite particles, whereas agriculture‐dominated sites produced smaller but more tightly compacted particles. Organic plant fibres appeared to play a vital role in floc formation in peat‐covered catchments, whereas in agriculture‐dominated catchments, land use‐derived aggregates dominated the composition. This study provides empirical evidence of the importance of effective particle size measurement in understanding the dynamics of suspended particulate matters in boreal lowland river systems. Copyright © 2014 John Wiley & Sons, Ltd.     

Suspended particulate grain size dynamics and their implications for trace metal sorption in the Don River

We examined particle size distributions of suspended particulate matter (SPM); physical and environmental influences on the observed distributions; and relationships between particle size and geochemical partitioning of metals, over the fall and winter period in a small urban river (Don River, Toronto, Ontario, Canada). For this dataset, the majority of particles (80%) in suspension were less than 10 µm in size. In addition, while total SPM concentrations showed a positive trend with increasing discharge (Q); the proportions of particles found within given size classes were independent of both SPM concentration and Q. Temperature was the only measured environmental variable related to the particle concentrations within size classes. As water temperature increased, the concentration of particles in the smallest size class (1–4 µm) decreased, while the concentration of silt and/or algae sized particles (10–50 µm) increased. Increasing water temperatures may promote bacterial attachment to particles and their subsequent flocculation into larger sized particles. Decreasing concentrations of leachable (most labile) Cd, Zn and Mn were associated with increasing concentrations of the largest particles (70–150 µm) in suspension. In contrast, higher reducible (oxides) associated concentrations of Cd, Zn and Mn occurred with increasing concentrations of smaller particles (1–10 µm) in suspension. Both of these trends are speculated to reflect the importance of particle surface area for metal sorption reactions.     

Characterization of colloidal and particulate matter transported by the magela creek system,Northern Australia

The composition and amount of colloidal and suspended participate matter transported during a small flood event in Magela Creek in tropical northern Australia was investigated. The flood studied constituted approximately 3 % of the total annual flow, most (90%) of which occurred between mid-January and mid-February of the study year. Three fractions were separated from water samples using a sequential method involving a continuous flow centrifuge to separate suspended particulate matter (SPM; nominally > 1 μm) followed by hollow fibre filtration, first using a 0.1 μm filter to separate course colloidal matter (CCM; nominal size 1–0.1 μm) and then a 0–015 μm filter to separate fine colloidal matter (FCM; nominal size 0.1–0.015 μm). The SPM was predominantly inorganic (organic matter 21 %), whereas the colloidal fractions were dominantly organic matter (CCM 60%; FCM 83%). Analysis of individual particles using electron microprobe and automated image analysis indicated that the mineral fractions in both the SPM and CCM were dominated by iron-enriched aluminosilicates (including kaolinite) (72–82%) and quartz (9–10%), indicative of a highly weathered and extensively laterized catchment. Surprisingly there was very little difference in the composition of the SPM or CCM fractions during the flood event studied, which may indicate either that sediment availability was restricted following the major run-off events in January and February, or that all the sediment sources within the catchment are geochemically similar. Approximately the same amounts of particulate (20 tonne), colloidal (21 tonne) and dissolved material (17 tonne) were transported during the 25 hour period of the main flood peak; over 90% of the colloidal matter was 0.1–1.0 μm in size. These data suggest that previous estimates of the amounts of particulate (and colloidal) matter transported by Magela Creek, which were based on suspended solids measurements, may have underestimated the particulate matter load by as much as 50%. It is possible that the relatively high proportion of colloidal matter is unique to Magela Creek because coagulation and aggregation of colloidal matter to particulate matter is slow due to the very low concentations of calcium and magnesium in these waters. However, if the result is more widespread, there are important implications for the global estimates of fluvially transported particulate and dissolved materials as many of the previous studies may have underestimated the particulate load and overestimated the dissolved load.     

Some aspects of vanadium and chromium chemistry in the English Channel

Dissolved and particulate vanadium and chromium concentrations along a transect between Cherbourg and the Isle of Wight were investigated in the English Channel. Seawater samples were collected at two different depths (surface and bottom) at five sampling stations during five cruises carried out between September 1994 and September 1995. Calculated mass flows through this Channel section were 7600 T yr⁻¹ for vanadium (about 66% was in the dissolved phase) and 1650 T yr⁻¹ for chromium (about 50% was in the dissolved phase). Dissolved chromium concentrations do not vary significantly along the transect. Seasonal variations in chromium distribution linked to biotic parameters were noted during the September 1994 cruise, when a significant relationship between particulate chromium and algal organic carbon was found. In addition, dissolved Cr (III) and Cr (VI) were well correlated with both algal and terrestrial organic matter. In the May cruise, during phytoplanktonic decay, particulate chromium was correlated with the detritic and bacterial organic fractions. These observations suggest interactions between chromium and biotic material. During the winter period, no relationship between chromium and POC was found. Dissolved and particulate vanadium concentrations varied, respectively, between 15 and 28 nmol l⁻¹ and 2–32 nmol l⁻¹. Values of dissolved vanadium showed depletion in the Channel with respect to oceanic waters. This loss in dissolved vanadium was higher near the English coast, but was compensated for by the increase in the particulate vanadium. There was no clear relationship between dissolved vanadium and algal organic carbon and it is inferred that the vanadium transfer cannot be explained by trapping with biotic material. On the other hand, the dissolved vanadium depletion could be attributed to the presence of ferric oxyhydroxide phases in particles, which have strong adsorbing properties for a range of dissolved metal ions.     

Effects of overlying velocity,particle size,and biofilm growth on stream–subsurface exchange of particles

Stream–subsurface exchange strongly influences the transport of contaminants, fine particles, and other ecologically relevant substances in streams. We used a recirculating laboratory flume (220 cm long and 20 cm wide) to study the effects of particle size, overlying velocity, and biofilm formation on stream–subsurface exchange of particles. Sodium chloride was used as a non‐reactive dissolved tracer and 1‐ and 5‐µm fluorescent microspheres were used as particulate tracers. Surface–subsurface exchange was observed with a clean sand bed and a bed colonized by an autotrophic–heterotrophic biofilm under two different overlying velocities, 0·9 and 5 cm s^?1. Hydrodynamic interactions between the overlying flow and sand bed resulted in a reduction of solute and particle concentrations in the water column, and a corresponding accumulation of particles in both the sediments and in the biofilm. Increasing overlying velocity and particle size resulted in faster removal from the overlying water due to enhanced mass transfer to the bed. The presence of the biofilm did not affect solute exchange under any flow condition tested. The presence of the biofilm significantly increased the deposition of particles under an overlying velocity of 5 cm s^?1, and produced a small but statistically insignificant increase at 0·9 cm^?1. The particles preferentially deposited within the biofilm matrix relative to the underlying sand. These results demonstrate that hydrodynamic transport conditions, particle size, and biofilm formation play a key role in the transport of suspended particles, such as inorganic sediments, particulate organic matter, and pathogenic microorganisms in freshwater ecosystems, and should be taken into consideration when predicting the fate and transport of particles and contaminants in the environment. Copyright © 2009 John Wiley & Sons, Ltd.     

Unusual grain size effect on trace metals and organic matter in contaminated sediments

Grain size effect on trace metals (cadmium, copper, lead, zinc, and iron) and total organic content distribution in various fractions (<0.063, 0.063–0.105, 0.105–0.250, 0.250–0.500, and 0.500–1.000 mm) of contaminated sediment has been studied. Selective partitioning of the studied contaminants in sediment fractions was observed, with a minimum content in the fine sand fraction of grain size 0.125–0.250 mm. Anomalously high concentrations of trace metals and organic matter content in the medium and coarse sediment fractions (>0.250 mm) was explained by the formation of large agglomerates (clusters) during the generally recommended drying procedures. These large agglomerates, formed from smaller sediment fraction particles enriched by various contaminants kept on their large specific area by adsorption forces, have been observed in photographs of the medium and coarse sediment fractions only. The formed agglomerates consist of small particles cemented either by dissolved organic matter or by sea salts present in the marine sediment. The formation of such agglomerates should be taken into consideration when conducting metal contamination studies on sediments.     

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

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

Carbon and nitrogen cycling in the Zhubi coral reef lagoon of the South China Sea as revealed by Po and Pb

The radionuclides ²¹⁰Po and ²¹⁰Pb were examined to trace the cycling of particulate organic carbon (POC) and particulate organic nitrogen (PON) in the Zhubi coral reef lagoon. The net export flux of POC to the open sea is 14 mgC m⁻² d⁻¹. However, the net exchange of PON has not yet been observed. On average, the vertical export fluxes in the lagoon of POC and PON, as derived from ²¹⁰Po/²¹⁰Pb disequilibria, are 43 mgC m⁻² d⁻¹ and 13.8 mgN m⁻² d⁻¹, respectively. The deficit of ²¹⁰Po relative to ²¹⁰Pb in particulate matter provides evidence for the degradation of particulate organic matter. According to the mass balance budgets, 310 mgC m⁻² d⁻¹ and 121 mgN m⁻² d⁻¹ were recycled into dissolved fractions. Based on a first-order kinetics model, the degradation rate constants of POC and PON are 0.28 and 0.30 m⁻¹, respectively. Thus, ²¹⁰Po and ²¹⁰Pb can quantify the cycling of carbon and nitrogen in this coral lagoon.     

Distribution of dissolved and labile particulate trace metals in the overlying bottom water in the vistula river plume (southern Baltic Sea).

Overlying bottom water samples were collected in the Vistula River plume, southern Baltic Sea, (Poland) and analysed for dissolved and labile particulate (1 M HCl extractable) Cu, Pb, Zn, Mn, Fe and Ni, hydrological parameters being measured simultaneously. Particulate organic matter (POM), chlorophyll a and dissolved oxygen are key factors governing the chemical behaviour of the measured metal fractions. For the dissolved Cu, Pb, Zn, Fe and Ni two maxima, in the shallow and in the deeper part of the river plume, were found. In the shallow zone desorption from seaward fluxing metal-rich riverine particles account for markedly increased metal concentrations, as confirmed also by high particulate metal contents. For Pb, atmospheric inputs were also considered to have contributed to the elevated concentrations of dissolved Pb adjacent to the river mouth. In the deep zone desorption from detrital and/or resuspended particles by aerobic decomposition of organic material may be the main mechanism responsible for enrichment of particle-reactive metals (Cu, Pb, Zn) in the overyling bottom waters. The increased concentrations of dissolved Fe may have been due to reductive dissolution of Fe oxyhydroxides within the deep sediments by which dissolved Ni was released to the water. The distribution of Mn was related to dissolved oxygen concentrations, indicating that Mn is released to the water column under oxygen reduced conditions. However, Mn transfer to the dissolved phase from anoxic sediments in deeper part of the Vistula plume was hardly evidenced suggesting that benthic flux of Mn occurs under more severe reductive regime than is consistent with mobilization of Fe. Behaviour of Mn in a shallower part has been presumably affected by release from porewaters and by oxidization into less soluble species resulting in seasonal removal of this metal (e.g. in April) from the dissolved phase. The particulate fractions represented from about 6% (Ni) and 33% (Mn, Zn, Cu) to 80% (Fe) and 89% (Pb) of the total (labile particulate plus dissolved) concentrations. The affinity of the metals for particulate matter decreased in the following order: Pb > Fe > Zn > or = > Cu > Mn > Ni. Significant relationships between particulate Pb-Zn-Cu reflected the affinity of these metals for organic matter, and the significant relationship between Ni-Fe reflected the adsorption of Ni onto Fe-Mn oxyhydroxides. A comparison of metal concentrations with data from other similar areas revealed that the river plume is somewhat contaminated with Cu, Pb and Zn which is in agreement with previous findings on anthropogenic origin of these metals in the Polish zone of southern Baltic Sea.     

Organic carbon release by phytoplankton and bacterial reassimilation

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

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

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

Organically Bound Nutrients in Dissolved Organic Matter Fractions in Seepage and Pore Water of Weakly Developed Forest Soils

Previous field and laboratory studies showed that organically bound nutrients can contribute largely to the export of N, P, and S from soil into aquatic systems. One possible determinant for the losses of dissolved organic nutrients leaving the soil environment could be their distribution between dissolved organic matter (DOM) fractions of different mobility in soil. To elucidate the potential influence of DOM fractions under varying flow conditions on the vertical translocation of organically bound nutrients, we determined the concentrations and fluxes of dissolved organic C (DOC) and nutrients (DON, DOP, DOS) in soil water under a Scots pine (Pinus sylvestris L.) and a European beech (Fagus sylvatica L.) forest. We sampled seepage water from the organic forest floor layer and the mineral subsoil using zero‐tension lysimeters and soil pore water using tension lysimeters and suction cups. DOM in soil water was fractionated into hydrophilic and hydrophobic compounds by XAD‐8 at pH 2. We found that the organic forest floor layers were large sources for DOC, DON, DOP, and DOS. The dissolved organic nutrients were mainly concentrated in the hydrophilic DOM fraction which proved to be more mobile in mineral soil pore water than the hydrophobic one. Consequently, the concentrations and fluxes of dissolved organic nutrients decreased less with depth than those of DOC. Concentrations as well as fluxes in subsoil pore water of DOC and dissolved organic nutrients in the studied weakly developed soils were high as compared with literature data on deeply developed forest soils. Under conditions of rapid water flow through the strongly structured mineral soil at the beech site, almost no retention of DOM took place and thus the influence of the distribution of organically bound nutrients between the DOM fractions on the export of DON, DOP, and DOS was negligible.     

Seasonal and spatial variation in suspended matter,organic carbon,nitrogen, and nutrient concentrations of the Senegal River in West Africa

The Senegal River is of intermediate size accommodating at present about 3.5 million inhabitants in its catchment. Its upstream tributaries flow through different climatic zones from the wet tropics in the source area in Guinea to the dry Sahel region at the border between Senegal and Mauritania. Total suspended matter, particulate and dissolved organic carbon and nitrogen as well as nutrient concentrations were determined during the dry and wet seasons at 19 locations from the up- to downstream river basin. The aims of the study were to evaluate the degree of human interference, to determine the dissolved and particulate river discharges into the coastal sea and to supply data to validate model results. Statistical analyses showed that samples from the wet and dry season are significantly different in composition and that the upstream tributaries differ mainly in their silicate and suspended matter contents. Nutrient concentrations are relatively low in the river basin, indicating low human impact. Increasing nitrate concentrations, however, show the growing agriculture in the irrigated downstream areas. Particulate organic matter is dominated by C4 plants during the wet season and by aquatic plankton during the dry season. The total suspended matter (TSM) discharge at the main gauging station Bakel was about 1.93 Tg yr⁻¹ which is in the range of the only available literature data from the 1980s. The calculated annual discharges of particulate organic carbon (POC), dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) are 55.8 Gg yr⁻¹, 54.1 Gg yr⁻¹, and 5.3 Gg yr⁻¹, respectively. These first estimates from the Senegal River need to be verified by further studies.     

Particle Size Distribution Analysis of Chemical Oxygen Demand Fractions with Different Biodegradation Characteristics in Black Water and Gray Water

The study investigated the particle size distribution of major organic pollutants in black water and gray water fractions of domestic sewage. Particle size distribution was assessed by means of a filtration/ultrafiltration sequence together with laser diffraction. Emphasis was placed upon the correlation between the size distribution of chemical oxygen demand (COD) and its biodegradation characteristics obtained by respirometric analysis. Particle size distribution analysis provided specific fingerprints for COD, total organic carbon (TOC), carbohydrates, proteins, and color for black water and gray water: Aside from significant difference between COD contents, the more concentrated COD was predominantly in particulate form in black water, whereas soluble COD accounted for nearly 60% of the total in gray water. TOC and carbohydrate exhibited a similar pattern. Size distribution of particulate matter yielded different characteristics for the two fractions and indicated that settleable matter should be considered as a significant portion in assessing biodegradation. Particle size distribution of COD, although not directly related, gave an accurate image of biodegradation, indicating that particle size was basically the main parameter for differentiating and predicting major COD fractions with different biodegradation characteristics. It explained the dual hydrolysis mechanism associated with the black water based on the existence of a significant settleable COD fraction.     

Sources of particulate and dissolved organic carbon in the St Lawrence River: isotopic approach

We investigate sources of both dissolved and particulate organic carbon in the St Lawrence River from its source (the Great Lakes outlet) to its estuary, as well as in two of its tributaries. Special attention is given to seasonal interannual patterns by using data collected on a bi‐monthly basis from mid‐1998 to mid‐2003. δ¹³C measurements in dissolved inorganic carbon, dissolved organic carbon (DOC) and particulate organic carbon (POC), as well as molar C : N in particulate organic matter (POM), are used to bring insight into the dynamic between aquatic versus terrigenous sources. In addition, ¹⁴C activities of DOC were measured at the outlet of the St Lawrence River to its estuary to assess a mean age of the DOC exported to the estuary. In the St Lawrence River itself, aquatically produced POC dominates terrestrially derived POC and is depleted in ¹³C by approximately 12‰ versus dissolved CO₂. In the Ottawa River, the St Lawrence River's most important tributary, the present dataset did not allow for convincing deciphering of POC sources. In a small tributary of the St Lawrence River, aquatically produced POC dominates in summer and terrestrially derived POC dominates in winter. DOC seems to be dominated by terrestrially derived organic matter at all sampling sites, with some influence of DOC derived from aquatically produced POC in summer in the St Lawrence River at the outlet of the Great Lakes and in one of its small tributaries. The overall bulk DOC is relatively recent (¹⁴C generally exceeding 100% modern carbon) in the St Lawrence River at its outlet to the estuary, suggesting that it derives mainly from recent organic matter from topsoils in the watershed. Copyright © 2005 John Wiley & Sons, Ltd.     

UV spectrometry for measuring particulate organic matter in natural water

Ultraviolet (UV) spectra were measured to characterize the dissolved and particulate organic matter in a bog and to investigate the seasonal fluctuation of this organic matter. The optical density spectra in the UV region of dissolved organic matter (DOM) were proportional to ^–4, where is the wavelength of incident light. There was also small absorption on the ^–4 spectra. The optical density at a wavelength of 280 nm was proportional to the concentration of dissolved organic carbon (DOC). The spectra and the dependency of optical density on DOC did not vary throughout the investigation period. The UV spectra of acid extractions of particulate organic matter (POM) showed two absorption peaks at the wavelengths of 220 nm and 335 nm. These peaks are well represented by the sum of two Lorentz functions. The ratio of the absorbances,A ₂₈₀/A ₃₃₅, was dependent on the nitrogen/carbon ratio of POM and the chlorophyll fraction in particulate organic carbon (POC), and not dependent on POC itself. The dependency of POC absorption at 280 nm varied with this ratio which fluctuated seasonally.     

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

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