Distribution of trace metals in the Odra River system: Water–suspended matter–sediments

Extensive investigations of trace metals concentrations in water, suspended particulate matter (SPM) and bottom sediments of the whole Odra River system were carried out over the years 1997–2000. The vertical distribution of selected metals and their mobility were also studied in the sediment cores from upper and middle river sections. Significant levels of metal contamination were found. Median concentrations (Cd, Pb, Cu, Zn and As) in the SPM and sediments were (mg kg⁻¹) 7.1 and 8.9 Cd, 128 and 146 Pb, 81 and 119 Cu, 1198 and 1204 Zn, 48 and 54 As, respectively. The highest metal pollution of the Odra River solids was found with cadmium, zinc, lead and arsenic, showing high similarity in their frequency distributions in both SPM and sediments. Cd, Zn and As appear to be of particular concern because of the high levels, that appear to be bioavailable, and their high mobility. The exchangeable and carbonate chemical forms of Cd and Zn reached up to 50% of their total amount. Besides the determination of total metal concentration, the metal chemical forms in river solids were investigated. The results of very wide studies of the Odra River system through 4 years suggest that metal pollution decreased, especially for Zn, Pb and Cu. Among all metals studied in the Odra River sediments, substantial reductions of Cd contamination were observed neither in the period after ’97 flood, nor if compared with the earlier results obtained before ’97. No essential differences of the metal contents were observed among the samples for the same river compartment, from the same locality, taken within the five sampling campaigns. The pattern of spatial and vertical metal distributions in the river solids indicates that a variety of sources might be responsible for the contamination; very intensive, historical and current mining and smelting activities probably are the most important ones.     

The Flood in the Odra River 1997 – Impact of Suspended Solids on Water Quality

The flood in the Odra river in 1997 has led to considerable additional pollution of the Stettin Lagoon and the Baltic Sea with contaminated suspended solids. For some priority substances, the pollutant entries via suspended solids during the flood period are estimated to be approximately 1/3 of the usual annual load. Among these priority pollutants there are total organic carbon (TOC), nitrogen, and the heavy metals Cu, Pb and Zn. For the concentrations of the priority pollutants in suspended solids accumulation factors from 2 to 4 in the comparison with normal conditions were observed. On the basis of the analysis of sediments sampled after the flood, main sources of the pollutants should be evaluated. As reference area with an industrial background as well as a typical pollutant pattern the region around Glogow/Legnica is proposed.     

The Pollution Load from the River Odra in Comparison to That in Other Polish Rivers in 1988–1997

The discharge of organic matter, nutrients, and heavy metals from the river Odra into the Baltic Sea is compared with the combined discharge of the same substances from other Polish rivers into the Baltic during 1988–1997. The impact of the summer flood of 1997 is also discussed. The discharges of organic matter, nitrogen and phosphorus compounds were closely correlated with the flow rate. The annual loads of these nutrients measured in 1988 and 1996 under similar flow conditions decreased by 15 to 40% in these rivers as a result of the reduction of point sources. A steady decrease in the heavy metal load, independent of weather conditions, has been recorded during the past decade. Zinc decreased by up to 85% in the Odra and 99% in the Wisła. Although the water outflow from the Odra was half that of the Wisła, it transported a proportionally higher load of chemical compounds. Despite the differences in flow rates, the contribution of both rivers to the total riverine phosphorus discharge was approximately the same. The total water outflow during the flood (from 1 July to 28 August 1997) increased by 65% near the mouth of the Odra in comparison to 1996. The phosphate discharge increased by 34%, that of nitrite nitrogen by 88%     

Assessment of Water Quality in the Elbe River at Flood Water Conditions Based on Cluster Analysis,Principle Components Analysis,and Source Apportionment

An assessment of water quality measurements during a spring flood in the Elbe River is presented. Daily samples were taken at a site in the middle Elbe, which is part of the network of the International Commission for the Protection of the Elbe River (IKSE/MKOL). Cluster analysis (CA), principal components analysis (PCA), and source apportionment (APCS apportioning) were used to assess the flood‐dependent matter transport. As a result, three main components could be extracted as important to the matter transport in the Elbe River basin during flood events: (i) re‐suspended contaminated sediments, which led to temporarily increased concentrations of suspended matter and of most of the investigated heavy metals; (ii) water discharge related concentrations of pedogenic dissolved organic matter (DOM) as well as preliminary diluted concentrations of uranium and chloride, parameters with stable pollution background in the river basin; and (iii) abandoned mines, i.e., their dewatering systems, with particular influence on nickel, manganese, and zinc concentrations.     

Input-output Balances of Nutrients and Plankton in a Flooded Area of the Lower Odra

The retention of particulate matter of the Odra River in flooded areas was estimated by determining suspended particulate matter (SPM) elimination and particle-bound nutrient retention in a polder area of the Lower Odra Valley national park. Water and suspended matter samples collected before, during, and after the 1997 summer flood at the inlet and the outlet of the investigated polder (Polder A/B close to Schwedt) offer the opportunity to balance the matter retention inside the floodplain. The maximum level of retained SPM (more than 80%) was calculated for the record flood of summer 1997, while in ordinary winter floods retention differs between 33% and 70%. Basic properties of the flowing particles like settling velocity, density, loss on ignition etc. change on their way through the polder area. In the investigated Polder A/B a retention of at least 50% of particle-bound phosphorus which was independent of the incoming suspended matter load from the Odra River was observed. The retention of particle-bound nitrogen and carbon varied seasonally to different extents. The presented balance demonstrates that particle-bound nutrient retention in polders is an important factor in the self-purification process of the river system. Some additional effort was done to study changes of plankton composition: during a joint field experiment in spring 1998, the authors determined biological parameters (abundance and biomass of phytoplankton and zooplankton) of water samples at polder inflow and outflow points.     

Copper,zinc, cadmium,nickel, iron and manganese in the Southern Bight of the North Sea

Ni, Cd, Cu, Zn, and Fe were determined in water and suspended matter samples and Mn in suspended matter samples from the Southern Bight region of the North Sea. Four distinct areas, comprising the Rhine estuary, the Dutch coastal waters, the centre of the Bight, and the English coastal water can be distinguished on the basis of the distribution of the trace metals. The total concentrations of all metals were high in the Rhine estuary, decreased in a seaward direction to reach very low values, comparable to continental shelf water, in the centre of the Bight, and increased again towards the English coast. Elevated concentrations of dissolved Cu, Ni, Cd and Zn near the English coast are not only due to river inputs. Over the entire region, the fraction of Cd, Ni and Zn in solution was consistently more important than the fraction in the suspended particulate phase. In contast, the fraction of Fe and Mn in the solid phase was consistently greater than the fraction in solution. Total concentrations of Fe, Mn and Cu are more dictated by the suspended particulate matter concentration than Cd, Ni and Zn.     

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.     

Investigations on Mineralogical and Chemical Composition of Suspended Particulate Matter (SPM) in the Odra Estuary

In order to recognize lateral and seasonal variations in composition of suspended particulate matter (SPM) in the Odra Estuary, samples were taken at four sites in the period July 1996 - July 1997 monthly if possible. The contents of the elements Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, P, C, S as well as Ba, Cr, Sr, V, Zn, Cu, Zr, and of the minerals illite, chlorite, smectite, kaolinite and others have been determined. The decreasing influence of the river Odra towards the open sea could be realized with the help of the contents of the minerals quartz, smectite, and of the elements Ba, Cr, K, P, Si and other. 60% of the seasonal and lateral variations can be explained by changing contents of total carbon (TC), total organic carbon (TOC), Al, Fe, Si, Ti, P, Mn, and Ba. They are mainly caused by differences in the production of organic matter, resuspension, riverine input, and redox-sensitive processes.     

Ecological Conditions of Watercourses in the Middle Amur Lowland in the Areas of Drainage Reclamation

The effect of land reclamation on the migration and accumulation of heavy metals and some pollutants in small rivers is determined. The study was conducted in the Middle Amur lowland in different phases of hydrological regime and at different extent of floodplain inundation. The formation of the hydrological regime in small rivers in this area is governed by the irregular annual runoff distribution. The seasonal character of flood periods requires water samples to be taken before spring flood (April) and after floods have passed (September–October), and at various extent of floodplain inundation. The field studies of water-courses were carried out in 2009–2014. The water samples were analyzed to determine the concentrations of heavy metals (iron, manganese, copper, nickel, cobalt, lead and zinc), suspended substances, organic carbon (total, dissolved, and suspended), humic and fulvic acids, and volatile organic compounds. The mobility of heavy metals in surface watercourses was shown to reflect the effect of drainage and surface runoff from soil horizons, an increase in the concentrations of suspended and organic compounds, especially, fulvic acids, which enhance their geochemical mobility. During floods, an increase in heavy metals washout from floodplain soils and the dilution of their concentrations causes the formation of a single-type concentration series of heavy metals. In addition, the processes of pollutants migration show an effect of changes in the geomorphological characteristics of floodplain–channel complexes and a decrease in flow velocity in watercourses in the areas where land reclamation was applied. Thus, all factors mentioned above lead to a decrease in water pollution index in the river.     

Mercury distribution in Douro estuary (Portugal)

Determinations of dissolved reactive and total dissolved mercury, particulate and sedimentary mercury, dissolved organic carbon (DOC), particulate organic carbon (POC) and suspended particulate matter (SPM) have been made in the estuary of river Douro, in northern Portugal. The estuary was stratified by salinity along most of its length, it had low concentrations of SPM, typically <20 mg dm(-3), and concentrations of DOC in the range <1.0-1.8 mg dm(-3). The surface waters had a maximum dissolved concentration of reactive mercury of about 10 ng dm(-3), whereas for the more saline bottom waters it was about 65 ng dm(-3). The surface waters had maximum concentrations of total suspended particulate mercury of approximately 7 microg g(-1) and the bottom waters were always <1 microg g(-1). Concentrations of mercury in sediments was low and in the range from 0.06 to 0.18 microg g(-1). The transport of mercury in surface waters was mainly associated with organic-rich particulate matter, while in bottom waters the dissolved phase transport of mercury is more important. Lower particulate organic matter, formation of chlorocomplexes in more saline waters and eventually the presence of colloids appear to explain the difference of mercury partitioning in Douro estuarine waters.     

Heavy metal inflow into the floodplains at the mouth of the river Weiße Elster (Central Germany)

From 1998 to 2002 investigations were carried out to estimate both the quantity and quality (heavy metal contents) of suspended matter loads discharged into a floodplain area measuring approx. 5 km² of the Central German river Weiße Elster, a tributary of the river Saale in the Elbe river basin. Flood sediments, suspended particulate matter, and floodplain soils were investigated especially for the main pollutants Cd, Zn, Cu, Pb, Cr, and Hg. Supplementary gamma spectroscopy examinations were performed to help to identify the age of deposits in order to estimate sedimentation rates for last decades. The recent flood sediments are contaminated by up to 33 times the geogenic background (Cd). Up to 55% of the total annual SPM load of the river Weiße Elster is relocated into the investigated retention area in the flood‐stricken year 2002. The sedimentation rates for the last 50 years vary between 0.5 mm/a and 1 mm/a in far away and rarely flooded parts and between 1 mm/a and 2 mm/a in the frequently flooded parts of the inflow of the retention area.     

The Comparison of Sediment Contamination in the Area of Estuary and the Lower Course of the Odra Before and After the Flood of Summer 1997

The concentration of heavy metals (Hg, Cd, Pb, Cu, Zn, Cr, Ni, Mn) and chloroorganic substances (γ-HCH, ΣDDT, PCB) in surface sediments of the Western and the Eastern Odra River was analyzed after the 1997 flood and compared with data from 1995. The research has shown that, like in 1995, the Western Odra sediments were more contaminated with heavy metals and PCBs than the Eastern Odra ones. In comparison with the state of 1995, after the flood in both arms of the Odra, the amount of Cr, Mn, and PCBs has increased while the amount of Pb concentration decreased. The levels of Cd, Zn, and Ni have remained unchanged. The changes of the other pollutants were not so clear. The concentration of Hg and Cu increased in the Western Odra, while it decreased in the Eastern Odra; changes of γ-HCH and ΣDDT content were inverted.     

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.     

Studying the biogenic and abiogenic parts of suspended particulate matter in the Volga delta during spring flood of May 2008

Multidisciplinary studies of the dispersed sedimentary matter (suspended particulate matter) were carried out in the Volga delta during spring flood in two areas of the Astrakhan State Biosphere Reserve (Obzhorovskii and Damchikskii), allowing the authors to reveal some regularities in sedimentation conditions. Considerable differences were found to exist in the supply of sedimentary material into the sea through the branches and arms of the eastern and western parts of the river delta. Typical of the eastern part are appreciably higher concentrations of suspended particulate matter, biogenic components, and phytopigments, as well as greater phytoplankton abundance and biomass, and sedimentary material fluxes. A relationship was found to exist between the concentration of suspended particulate matter and the phytopigments under consideration. In May, almost entire chlorophyll “a” in suspended particulate matter was concentrated in the cells of small diatom algae, where it was distributed in proportion to diatom biomass. Overall, the suspended matter of the delta is mostly represented by mineral detrital particles (quartz and carbonates) with a relatively small share of clay materials against the background of a huge amount of diatom cells and biogenic detritus.     

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.     

On the significance of wind event frequency for particulate resuspension and light attenuation in coastal waters

Wind-induced resuspension of particulate matter was investigated in a shallow coastal region off southwestern Australia, chosen for its isolation from the complexity of other confounding physical processes. The site had negligible river discharge, low nutrient concentrations and was largely devoid of tidal currents. Moorings were deployed in the micro-tidal waters to measure current speed, wave parameters, backscatter, subsurface irradiance and dissolved oxygen concentration. Two contrasting sites were chosen as representative of high and low wave-energy environments. Turbulent kinetic energy, recorded by the instruments, was dominated by the wind-wave signal. During wind events, at the most exposed site, bed shear stress exceeded the critical stress required to lift and resuspend sediments. At the most enclosed site, bed shear stresses only exceeded the critical stress required to suspend less dense material such as benthic fluff. Wind-waves were found to be the dominant mechanism driving the vertical redistribution of particulate matter. Low frequency storm events and high frequency (daily) sea breezes were found to differ significantly in their retention of particulate matter suspended in the water column. Long periods of calm generally followed the passage of a storm, allowing suspended particulate matter to settle out, while consecutive daily sea breezes were more effective in holding particulate matter in suspension. Linear correlations were found between the backscatter (a proxy for suspended particulate matter), light attenuation and dissolved oxygen concentration. Approximately half the variability in dissolved oxygen concentration could be attributed to the variability in light attenuation, with a decline in concentration during wind resuspension events. Variability in dissolved oxygen concentration was interpreted as a possible indicator of the moderation of pelagic phytoplankton productivity during wind events.     

Polycyclic Aromatic Hydrocarbons and Polysaccharides in River Sediments from the Odra Basin after the 1997 Flood

Fourteen polycyclic aromatic hydrocarbons (PAH), six monosaccharides (SA) formed following the hydrolysis of polysaccharides, as well as water and organic matter contents were determined in river sediments sampled in thirteen points in the Odra basin after the catastrophic flood of 1997. The water content is related to the water absorbing capacity of the soil in the Odra catchment area. The PAH content increases together with the increase in the organic matter (OM) content which suggests that these species are mainly of anthropogenic origin. On the other hand, SA and OM contents decrease with increasing water content, which implies that both enhance biological life. The PAH content tends to decrease when the SA content increases. This relation goes hand in hand with the quality of water resources, which is greater when the quantity of polysaccharides is higher.     

Dissolved and particulate trace metal fluxes through the central English Channel, and the influence of coastal gyres

Measurements of dissolved Cd, Co, Cu, Mn, Ni, Pb, and Zn have been made on a seasonal basis at five stations on a north–south transect across the central English Channel between Cherbourg and the Isle of Wight. Vertical and horizontal distributions of dissolved Cd, Pb, Cu and Zn are relatively uniform except for sampling sites near the English coast. Dissolved Mn and Co show increased concentrations in the English coastal waters, and for Mn the seasonal trend in concentration follows the pattern seen in the Strait of Dover with higher values in the late summer. Ni and Cu are higher in concentration on the English side, which reflects mainly riverine sources. Measurements were also made of particulate forms of the metals above plus particulate Al, Ca, Fe, Mg, Sr and Ti. Water column concentrations of particulate metals broadly follow the distribution of suspended particulate matter, with highest concentrations near the UK coast. Trace metal concentrations have been integrated with modelled data on fluxes of water to provide estimates of fluxes for these elements into the eastern Channel, and an initial comparison is made with data for fluxes of metals through the Strait of Dover obtained during an earlier study. A major influence on the fluxes of particulate metals through the Isle of Wight-Cherbourg transect is the gyre system to the South east to the Isle of Wight, which has important east to west as well as west to east transport components. For those elements where the dissolved form of the metal dominates, the large flow of water in the central Channel waters leads to major fluxes of the metals towards the east and the Strait of Dover. However, the high suspended particulate matter loadings in the coastal waters and impact of the gyre system lead to net east to west fluxes of particulate Al, Fe, Mn and Ti. Comparison of these fluxes with data on the net west to east transport of these materials through the Strait of Dover infers that there must be a significant supply of these particulate metals to the eastern Channel.     

Morphological Investigations in the River Odra

Since 1992, the Federal Institute of Hydrology (Bundesanstalt für Gewässerkunde – BfG) performs morphological investigations in the river Odra downstream from the confluence of the river Neiße (Nysa Luzycka). The results of these investigations give a clear insight into the morphodynamic behaviour of this part of the river and indicate that on average 380 000 t of suspended solids and 130 000 t of bed load are transported by the river Odra at Hohensaaten per year, with a distinct seasonal variability in the case of suspended solids. Detailed studies on type and composition of the bed substrates have revealed that the river bottom is composed of very fine material: at Ratzdorf already 75 % of the bed material is finer than 2 mm, at Widuchowa almost all of the river bed material consists of sand finer than 0.63 mm. Because of the high sensitivity of the river bottom to discharge increases and the corresponding increases of bottom shear stress sand was found to be the dominating fraction of the suspended load in case of extreme flood events.     

Total Organic Carbon (TOC) as a Sum Parameter of Water Pollution in Selected Polish Rivers (Vistula,Odra, and Warta)

This paper reports on total organic carbon (TOC) and its fractions dissolved organic carbon (DOC) and particulate organic carbon (POC) studied in different Polish rivers. The samples investigated came from the Vistula, Odra, and Warta rivers, and were compared with similar data on river waters available in the literature. The DOC concentrations ranged from 10.0 to 14.2 mg/L and did not vary during the vegetative season. The POC values considerably increased from May through September and reached a maximum in summer. Results for the years 1991τ1996 evidenced a significant increase in the POC value for the Polish rivers from 10.8 to 24.5 mg/L, in comparison with analogous values for West European rivers and North American ones. The enhanced values of TOC and POC were interpreted as being due to anthropogenic pollution.