Temporal dynamics of dissolved and particulate organic carbon in the northern Adriatic Sea in relation to the mucilage events

The accumulation of dissolved and particulate organic matter may play an important role in mucilage formation in the northern Adriatic. Distributions of dissolved and particulate organic carbon were therefore investigated during the period June 1999-July 2002, when massive mucilage events occurred: in the summer of 2000 and, to a greater extent, of 2002. The seasonal variations in dissolved organic carbon (DOC) concentrations were significant, doubling in summer (up to 150 micromol L(-1)) with respect to winter. The particulate organic carbon (POC) variations were also very large, with a less pronounced seasonal pattern compared to DOC, because the POC changes are much more dependent both on river discharges and on phytoplankton blooms. The comparison of the concentrations between the period before (March-May) and after the onset of mucilage events (June-August) showed that DOC, but particularly POC, were higher in the period before the event of 2002, more markedly in the surface waters of low salinity. The POC increased, reaching mean concentrations of up to 36 micromol L(-1) in March 2002 before the outbreak of the massive mucilage formation in June. This suggests that POC may have a more important role in the mucilage formation than DOC. The highest seasonal variations of organic matter concentrations took place in the upper layer of lower salinity, stressing the importance of stratification and pycnoclines for accumulation and aggregation of the organic matter in the northern Adriatic. The POC contribution to the total organic carbon was low in the oligotrophic waters (DOC/POC ratio >15) and increased with the phytoplankton biomass in the productive waters (DOC/POC ratio <10). Particulate organic carbon predominated over the dissolved inside the mucilage aggregate (DOC/POC ratio <1), probably because aggregation processes, in which colloidal organic carbon is involved, are important. The organic carbon within the aggregates reached a concentration of 13.6 mmol L(-1) which was about 100 times more than in the surrounding waters or in the waters when the mucilages were absent. This indicates that distributions of organic carbon in the northern Adriatic can be extremely patchy during mucilage events.     

Geochemical characteristics and fluxes of organic carbon in a human-disturbed mountainous river (the Luodingjiang River) of the Zhujiang (Pearl River), China

This study aims to investigate the state of the riverine organic carbon in the Luodingjiang River under human impacts, such as reforestation, construction of reservoirs and in-stream damming. Seasonal and spatial characteristics of total suspended sediment (TSS), dissolved organic carbon (DOC) and particulate organic carbon (POC), as well as C/N ratios and the stable carbon isotopic signatures of POC (δ¹³C_POC) were examined based on a one-year study (2005) in the basin-wide scale. More frequent sampling was conducted in the outlet of the river basin at Guanliang hydrological station. DOC and POC concentrations showed flush effects with increasing water discharge and sediment load in the basin-wide scale. Atomic C/N ratio of POC had a positive relationship with TSS in the outlet of the basin, indicating the reduced aquatic sources and enhanced terrestrial sources during the high flood season. However, the similar relationship was not observed in the basin-wide scale mainly due to the spatial distributions of soil organic carbon and TSS. δ¹³C_POC showed obvious seasonal variations with enriched values in the period with high TSS concentration, reflecting the increased contribution from C₄ plants with enhanced soil erosion.The specific flux of the total organic carbon (2.30 t km^− 2 year^− 1) was smaller than the global average level. The ratio of DOC to POC was 1.17, which is higher than most rivers under Asian monsoon climate regime. The organic carbon flux was estimated to decline with decreasing sediment load as a result of reforestation, reservoir construction and in-stream damming, which demonstrates the impacts of human disturbances on the global carbon cycle.     

Removal of viable bacteria in lake water by denim filtration

A series of experiments were performed to investigate the removal of viable bacteria [Escherichia coli, total coliforms and standard plate count (SPC) bacteria] in lake water by denim filtration. Filtration with indigo reagent‐dyed denim physically removed E. coli (up to 95%) and total coliforms (up to 92%) from lake water. The removal efficiencies of SPC bacteria (up to 85%) were generally lower than those of E. coli and total coliforms. The adsorption of bacteria to particulate matter larger than the effective pore size of the denim (ca. 48 μm) and the subsequent physical sieving of the large particulate matter seemed to be the dominant disinfection mechanism.     

Sorption and desorption behaviours of 2,4‐D and glyphosate in calcareous soil from Antalya,Turkey

2,4‐Dichlorophenoxyl acetic acid (2,4‐D) and glyphosate are used extensively as a herbicide in vicinity of Antalya, Turkey. Laboratory batch experiments were conducted to investigate the sorption isotherm and sorption‐desorption characteristics of 2,4‐D and glyphosate. Results indicated that degree of sorption of glyphosate was approximately 50 times higher than 2,4‐D (K_d= 34.43 vs. 0.66 L/Kg). The sorption of 2,4‐D and glyphosate was described by linear and rate‐limited processes for soil. Organic carbon content was most likely responsible for sorption behaviour of 2,4‐D and glyphosate. The rapid desorption can be attributed to soft carbon fraction (humic/fluvic acid and lipids) whereas slower desorption can be responsible by hard carbon fraction (black carbon, kerogen) of soils that led to chemically nonideal behaviour (hysteresis). Sorption of 2,4‐D was low due to most likely deactivation of organic carbon surfaces by excess carbonate fraction, whereas strong binding of glyphosate onto organic carbon causing high sorption behaviour.     

Carbon and nitrogen isotopic compositions of particulate organic matter and biogeochemical processes in the eutrophic Danshuei Estuary in northern Taiwan

The Danshuei Estuary is distinctive for the relatively short residence time (1-2 d) of its estuarine water and the very high concentration of ammonia, which is the dominant species of dissolved inorganic nitrogen in the estuary, except near the river mouth. These characteristics make the dynamics of nitrogen cycling distinctively different from previously studied estuaries and result in unusual isotopic compositions of particulate nitrogen (PN). The delta(15)N(PN) values ranging from -16.4 per thousand to 3.8 per thousand lie in the lower end of nitrogen isotopic compositions (-16.4 to +18.7 per thousand) of suspended particulate matter observed in estuaries, while the delta(13)C values of particulate organic carbon (POC) and the C/N (organic carbon to nitrogen) ratios showed rather normal ranges from -25.5 per thousand to -19.0 per thousand and from 6.0 to 11.3, respectively. There were three major types of particulate organic matter (POM) in the estuary: natural terrigenous materials consisting mainly of soils and bedrock-derived sediments, anthropogenic wastes and autochthonous materials from the aquatic system. During the typhoon induced flood period in August 2000, the flux-weighted mean of delta(13)C(POC) values was -24.4 per thousand, that of delta(15)N(PN) values was +2.3 per thousand and that of C/N ratio was 9.3. During non-typhoon periods, the concentration-weighted mean was -23.6 per thousand for delta(13)C(POC), -2.6 per thousand for delta(15)N(PN) and 8.0 for C/N ratio. From the distribution of delta(15)N(PN) values of highly polluted estuarine waters, we identified the waste-dominated samples and calculated their mean properties: delta(13)C(POC) value of -23.6+/-0.7 per thousand, delta(15)N(PN) value of -3.0+/-0.1 per thousand and C/N ratio of 8.0+/-1.4. Using a three end-member mixing model based on delta(15)N(PN) values and C/N ratios, we calculated contributions of the three major allochthonous sources of POC, namely, wastes, soils and bedrock-derived sediments, to the estuary. Their contributions were, respectively, 83%, 12% and 5% under non-typhoon conditions, and 9%, 63% and 28% under typhoon conditions. The autochthonous POM had the most varied isotopic compositions, encompassing the full ranges of delta(13)C(POC) (-25.5 to -19.1 per thousand), delta(15)N(PN) (-16.4-3.8 per thousand) and C/N ratio (6.0-11.3). The heavy end of the carbon isotopic composition reflected the typical marine condition and the lower end the estuarine condition, which probably had elevated concentrations of dissolved inorganic carbon with low delta(13)C values due to input from decomposition of organic matter. The lack of isotopically heavy PN, as found in larger estuaries, was attributed to isotopically light starting materials, namely, anthropogenic wastes, the slow phytoplankton growth within the estuary and the rather short residence time; the latter two factors made (15)N enrichment during ammonia consumption very limited. The most isotopically light PN likely originated from phytoplankton incorporating (15)N-depleted nitrate near the river mouth, where ammonia inhibition of nitrate uptake probably stopped.     

Sensitivity of blanket peat vegetation and hydrochemistry to local disturbances

At the ecosystem scale, peatlands can be extremely resilient to perturbations. Yet, they are very sensitive to local disturbances, especially mechanical perturbations (e.g. trampling). The effects of these disturbances on vegetation, and potential effects on hydrochemical conditions along the peat surface, however, are largely unknown.We used three research tracks (paths researchers use to access their study sites) differing in time of abandonment to investigate the impact of local disturbance (trampling) on the vegetation and its short-term (≤ 2 year) recovery in a flagship research blanket peatland. Additionally, we examined the effects of local disturbance on fluvial runoff events and the concentrations of dissolved organic carbon (DOC) and particulate organic carbon (POC) in runoff water.Local disturbance heavily impacted peat vegetation, resulting in large areas of scarred and churned peat. Recovery of vascular plants along abandoned tracks was slow, but a functional Sphagnum layer re-established after just one year.The absence of vegetation elicited an increase in the number of runoff events along the tracks, by which POC runoff from the tracks increased. POC concentrations were highest in the surface water from the recently abandoned track, while they were low in the runoff water from the track abandoned longest and the undisturbed control track. We attribute this to the relatively fast recovery of the Sphagnum vegetation. DOC concentrations did not differ significantly either spatially or temporally in surface runoff or soil solution waters.While at an ecosystem scale local disturbances may be negligible in terms of carbon loss, our data points to the need for further research on the potential long-term effects of local disturbance on the vegetation, and significant effects on local scale carbon fluxes. Moreover, the effects of disturbances could be long-lasting and their role on ecosystem processes should not be underestimated.     

Temporal variations in dissolved organic carbon concentrations in upland and lowland lakes in North Wales

Over a period of 18 months, the dissolved organic carbon (DOC) concentration of a series of four lakes in North Wales was measured monthly. The lake catchment profiles consisted of an upland thin peat/soil (Llyn Cwellyn), an upland thin peat/soil associated with an adjacent area of small bog (Llyn Teyrn), an upland blanket bog (Llyn Conwy), and large lowland fen and fertile agricultural area (Llyn Cefni). The results examine the indirect effect of temperature and precipitation on the DOC concentrations found in the lakes fed by the catchments. The lowest DOC of the four sites was observed for Llyn Teyrn, varying from 1.2 to 3.30 mg/L, and with the highest being recorded for Llyn Cefni (5.45–10.83 mg/L). Temperature and rainfall data were both collected. Correlations with the DOC exhibited significant relationships with temperature for three of the sampled lakes Cwellyn (r 0.490), Teyrn (r 0.640) and Cefni (r 0.472). Recomputation versus 30‐ and 60‐day temperature lag times improved the correlation coefficients. The data showed weak and insignificant correlations for DOC versus rainfall for the three lakes, but the upland lake, Llyn Conwy, with its blanket bog catchment, did not demonstrate any statistical correlation with temperature, although it did show a significant correlation for DOC versus rainfall (r 0.553, P < 0.05). Over the sampling period, although tentative relationships were found among temperature, rainfall and DOC levels, an indirect association tempered by site hydrology is suggested.     

Partitioning of trace metals between dissolved and particulate phases in a typical backwater system of Kerala,India

Concentrations of dissolved and particulate trace metals (Ni, Pb, Zn and Mn) and their partitioning behaviour between the dissolved and particulate phases in a typical backwater system of Kerala, viz. the southern upstream part of Cochin Estuarine System (South India), have been studied. Spatial and temporal variations of trace metals in the dissolved and particulate phases have been discussed with special reference to pH, dissolved oxygen, salinity and suspended particulate matter. The distribution and partitioning behaviour of trace metals in the water column were found influenced by the presence of a salinity barrier across the backwater system and also by the massive use of pesticides and chemical fertilizers in the vast area of agricultural land near the backwater system. Lack of proper flushing of the backwaters, which receive large amount of trace metals through the application of pesticides and agro‐chemicals, due to the presence of the salinity barrier has significantly affected the water quality of the area.     

Production of dissolved organic carbon in aquatic sediment suspensions

In many water quality models production of dissolved organic carbon (DOC) is modelled as mineralisation from particulate organic matter (POM). In this paper it is argued that the DOC production from dessicated sediments by water turbulence may be of similar importance. The DOC production from sediments was measured under sterile conditions, as a function of shaking time, sediment to water ratio and OC content. Furthermore, the maximum fraction of particulate organic carbon (POC) that can be mobilised by agitation (excluding the contribution of mineralisation) was assessed. The experiments can be considered as laboratory simulations of resuspension of aquatic sediments due to turbulence caused by wind, benthivorous fish or dredging. It was found that aquatic resuspension of dessicated sediment may cause mobilisation of up to 100% of indigenous particulate carbon in a few weeks. An empirical equation was derived that expresses mobilised carbon (DOC) as a function of sediment concentration (POC), OC fraction (f(OC)) and time. At a typical value of 25mg/L suspended sediment, the halflife for mobilisation is 0.5 day, which is much faster than bacterial degradation of POM in aquatic systems.     

n‐Alkane distributions in soil and water samples collected near Agbabu bitumen field of southwestern Nigeria

Soil and water samples from the vicinity of Agbabu bitumen field of Southwestern Nigeria were analysed by GC‐FID for n‐alkanes, in order to characterize their distributions and to gather information on the degree of contamination by bitumen exploration and processing and other biogenic contributions. Total concentrations of n‐alkanes in water and soil samples analysed ranged from 61.5 to 472.7 µg L^?1 and 422.8 to 2289.4 ng g^?1 dw, respectively. On the basis of the total n‐alkane concentrations, carbon preference index (CPI) values and the odd‐even carbon predominance, it is suggested that both natural (e.g. aquatic input) and anthropogenic (e.g. bitumen and synthetics) sources contribute to the n‐alkanes load in soil and water samples of the area studied.     

Impact on phytoplankton populations of sewage discharges in the Saronikos Gulf (West Aegean)

Temperature, salinity and concentrations of dissolved oxygen, nutrients, chlorophyll a, particulate carbon and nitrogen concentrations in sea water near the Keratsini sewage outfall are reported. Suggestions are made on the proposed length of the outfall diffuser and the extent of the sewage treatment. Eutrophication in the area around the outfall is demonstrated by enhanced chlorophyll a, particulate carbon and particulate nitrogen concentrations. For they provide evidence for high phytoplankton standing stock. However no appreciable differences in the inorganic nutrient levels between the outfall area and the normal background were observed. This suggests rapid uptake of nurients that/or effective dispersal from the outfall. The study indicates that in the case of oligotrophic waters and in the absence of the dissolved oxygen depletion, primary treatment may be preferable to secondary treatment.     

Lake restoration by dilution: Moses lake, Washington

Dilution water, low in macronutrients, was added to Moses Lake on three occasions in 1977 and once in 1978 during the spring-summer period. The addition resulted in reducing the annual average inflow concentration of phosphorus from about 130–140 μg l⁻¹ to 100 μg l⁻¹. The water exchange rate in Parker Horn, which is 8% of the lake volume, increased from about 1% day⁻¹ normally to 7 and 11% day⁻¹ for the May–September period in 1977 and 1978, respectively. Lake water was displaced at a predictable rate in the whole lake as well as the areas proximal to the input, as verified by specific conductance.Improvements in lake quality, compared to values from 1969–70, were rather good with greater reductions in algal biomass occurring than might have been expected to result from the less impressive reductions in total P content. Chlorophyll a decreased by about 60–80% and total P decreased by about 50–60%, depending on the area of the lake. However, Chl a averaged only 15 μg l⁻¹ during May–September 1978, while total P was rather high at 70–80 μg l⁻¹. The fraction of the phytoplankton composed by blue-green algae decreased from 96% in 1970 to 68% in 1977–78. The cause for the effect on biomass and species composition is unknown, but may be related to dilution of blue-green excretory products.A dilution water input of about 6 m³ s⁻¹ continuously during April–September would require 20% less total water and should provide adequate control of eutrophication in at least 30% of the lake volume proximal to the input and Parker Horn. That would provide an exchange rate of 5% day⁻¹ for Parker Horn and should achieve lake water residuals by midsummer of 50%. Two additional inputs to the lake are also proposed as two more phases in the restoration project.     

On the relationship between lake trophic level and lake sediments

The purpose of this work has been to study the relationship between lake type, as expressed by various trophic characteristics, and sediment type, as expressed by determinations of simple chemical data on nitrogen, phosphorus, carbon and loss on ignition. The study is based on two sets of data. The first one emanates from 71 lakes for which information is available from published sources on trophic level and N-content and organic content (loss on ignition) from surficial sediments. More detailed information has been obtained from 12 Swedish lakes/basins on the following water indicators of trophic level: transparency, chlorophyll-a, total-N, total-P, organic-N, inorganic-N. The sediment data from these 12 lakes include: mean values and characteristic values for organic content (loss on ignition, IG) C-, N- and P-contents from surficial sediments. A BPN-value (bioproduction number) is defined by the slope coefficient of the regression line between N-content and IG-content of surficial sediments (0–1 cm). It has been shown that the BPN-value provides most accurate information about lake trophic level on the scale from oligotrophy to eutrophy, provided that more than 50% of the lake area has lower loss on ignition than 20% (per dry substance). The BPN-value cannot be used as an indicator of trophic level if the IG-content is predominantly higher than 30% in a lake. In the latter case the ratio IG/N can be used as a means to differentiate lake humic level. The BPN-value, which is determined from sediment samples providing an even spread throughout the lake surface, yields lake typical information, whereas C/N ratios yield site specific information. A key diagrammatic interpretation between lake trophic type and lake sediments has been presented.     

Carbon budget for a British upland peat catchment

This study describes the analysis of fluvial carbon flux from an upland peat catchment in the North Pennines. Dissolved organic carbon (DOC), pH, alkalinity and calcium were measured in weekly samples, with particulate organic carbon (POC) measured from the suspended sediment load from the stream outlet of an 11.4-km(2) catchment. For calendar year 1999, regular monitoring of the catchment was supplemented with detailed quasi-continuous measurements of flow and stream temperature, and DOC for the months September through November. The measurements were used to calculate the annual flux of dissolved CO(2), dissolved inorganic carbon, DOC and POC from the catchment and were combined with CO(2) and CH(4) gaseous exchanges calculated from previously published values and the observations of water table height within the peat. The study catchment represents a net sink of 15.4+/-11.9 gC/m(2)/yr. Carbon flows calculated for the study catchment are combined with values in the literature, using a Monte Carlo method, to estimate the carbon budget for British upland peat. For all British upland peat the calculation suggests a net carbon sink of between 0.15 and 0.29 MtC/yr. This is the first study to include a comprehensive study of the fluvial export of carbon within carbon budgets and shows the size of the peat carbon sink to be smaller than previous estimates, although sensitivity analysis shows that the primary productivity rather than fluvial carbon flux is a more important element in estimating the carbon budget in this regard.     

Preparation and characterisation of new-polyaluminum chloride-chitosan composite coagulant

In this study, the formulation of a novel polyaluminum chloride-chitosan composite coagulant that improves the coagulation process for natural organic matter (NOM) removal was investigated. The performance of the composite coagulant was tested using two water sources (synthetic and natural water) to develop a better understanding on the behaviour of the composite coagulant. Fourier Transform-Infra red (FT-IR) spectroscopy, ferron analysis and zeta potential studies were performed to characterise the composite coagulant. FT-IR analysis showed that there is an intermolecular interaction between Al species and chitosan molecules, while ferron analysis indicated that the distributions of Al_a, Al_b, and Al_c in PACl-chitosan are different from those in PACl. At a low Al dosage (2.16 mg L⁻¹), a much higher removal of NOM from synthetic water, as evidenced from UV₂₅₄ and Dissolved Organic Carbon (DOC) measurements, was achieved by the composite coagulants in comparison to that removed by PACl or PACl and chitosan added separately. For natural water from the Myponga Reservoir, both polyaluminum chloride (PACl) and PACl-chitosan composite coagulants demonstrated similar dissolved organic carbon (DOC) percentage removal, whereas PACl-chitosan gave a slight improvement in removing the UV₂₅₄ absorbing components of NOM.     

Determination of particulate organic carbon in waters by the chemical oxidation method

Particulate organic carbon (POC) in waters was determined by chemical oxidation method which has been widely used for the determination of total organic carbon and/or dissolved organic carbon. In this method, a water sample was filtered through a filter paper and the paper was placed in a glass ampoule, followed by the determination of POC with a total carbon analyzer. This paper discussed the problems of carbon contamination dissolving from filter papers. The selection of filter papers, the carbon blank values resulting from the papers and the pretreatment of the papers were studied. It became clear that the glass-fiber filter paper pretreated at 500°C for 8 h was superior to the filter papers treated under other conditions. The POC's in waters were determined by this method, and the results agreed well with those obtained by an ordinary dry combustion method.     

Comparative study on organic constituents in polluted and unpolluted inland aquatic environments—II: Features of fatty acids for polluted and unpolluted waters

Fatty acids were analyzed for polluted river waters from the Tokyo area and unpolluted river, brook, reservoir and pond waters from the Ogasawara (Bonin) Islands to elucidate their features for polluted and unpolluted waters. Fatty acids ranging from the carbon chain length of C₈-C₃₄ including unsaturated and branched acids were found with the great predominance of even-carbon numbers and lower molecular weight ranges (C₁₃–C₁₉) in the water samples from the Tokyo area and Ogasawara Islands. It was thus confirmed that no marked changes in fatty acid composition between polluted and unpolluted waters are absent. However, the total contents of the acids (average, 270 ± 120 μg 1⁻¹ at 90% confidence limits) as well as the FAC (fatty acids as carbon)/TOC (total organic carbon, 2.6 ± 0.93%) and FAC/EOC (extractable organic carbon with ethyl acetate, 16 ± 6.7%) of river water samples from the Tokyo area were considerably higher than those of the waters from the Ogasawara Islands (58 ± 29 μg 1⁻¹, 0.79 ± 0.48% and 2.1 ± 0.51%, respectively). These higher values for the Tokyo area should be due to sewage.A filtering method showed that most of fatty acids (>95%) was present in particulate fractions. In addition, the content of free fatty acids was fairly lower than that of combined fatty acids. Further, unsaturated fatty acids were detected only in combined forms both in particulate and dissolved fractions. They are considered to be present as esters in polluted and unpolluted waters.     

Removal of aromatic compounds from water on biologically activated carbon

We have carried out an assessment of the content of aromatic compounds (o-nitrophenol, o-aminobenzoic acid) in grains of activated carbon of a biofilter at the stage of stationary water treatment. It was found that the removal degree of aromatic compounds by the biofilm of biologically activated carbon in great measure is determined by the value of the decreasing of Gibbs free energy of adsorption (−ΔG _a ). It is shown that due to the competing action of the biofilm part of the accessible surface of activated carbon is not used for adsorption of organic matter.     

Observed and modeled seasonal trends in dissolved and particulate Cu, Fe, Mn, and Zn in a mining-impacted stream

North Fork Clear Creek (NFCC) in Colorado, an acid-mine drainage (AMD) impacted stream, was chosen to examine the distribution of dissolved and particulate Cu, Fe, Mn, and Zn in the water column, with respect to seasonal hydrologic controls. NFCC is a high-gradient stream with discharge directly related to snowmelt and strong seasonal storms. Additionally, conditions in the stream cause rapid precipitation of large amounts of hydrous iron oxides (HFO) that sequester metals. Because AMD-impacted systems are complex, geochemical modeling may assist with predictions and/or confirmations of processes occurring in these environments. This research used Visual-MINTEQ to determine if field data collected over a two and one-half year study would be well represented by modeling with a currently existing model, while limiting the number of processes modeled and without modifications to the existing model's parameters. Observed distributions between dissolved and particulate phases in the water column varied greatly among the metals, with average dissolved fractions being >90% for Mn, approximately 75% for Zn, approximately 30% for Cu, and <10% for Fe. A strong seasonal trend was observed for the metals predominantly in the dissolved phase (Mn and Zn), with increasing concentrations during base-flow conditions and decreasing concentrations during spring-runoff. This trend was less obvious for Cu and Fe. Within hydrologic seasons, storm events significantly influenced in-stream metals concentrations. The most simplified modeling, using solely sorption to HFO, gave predicted percentage particulate Cu results for most samples to within a factor of two of the measured values, but modeling data were biased toward over-prediction. About one-half of the percentage particulate Zn data comparisons fell within a factor of two, with the remaining data being under-predicted. Slightly more complex modeling, which included dissolved organic carbon (DOC) as a solution phase ligand, significantly reduced the positive bias between observed and predicted percentage particulate Cu, while inclusion of hydrous manganese oxide (HMO) yielded model results more representative of the observed percentage particulate Zn. These results indicate that there is validity in the use of an existing model, without alteration and with typically collected water chemistry data, to describe complex natural systems, but that processes considered optimal for one metal might not be applicable for all metals in a given water sample.     

Copper addition by organic matter degradation in the freshwater reaches of a turbid estuary

This study reports on the relationship between copper (Cu) behavior and organic matter (OM) transformation along the turbidity gradient in the freshwater reaches of the Gironde Estuary. During a one-year survey, surface water and suspended particulate matter (SPM) were sampled at least monthly at three sites along the Garonne Branch, representing the main fluvial branch of the Gironde Estuary. Additionally, a longitudinal high resolution profile was sampled along the Garonne Branch, covering the turbidity gradient from the river water endmember to the maximum turbidity zone (MTZ). Seasonal variability and spatial distribution of Cu in both the dissolved phases (< 0.2 μm, Cu_0.2 and < 0.02 μm, Cu_0.02) and particulate Cu (Cu_P) clearly suggested Cu_0.2 addition during summer, that increased the Cu_0.2 concentrations by a factor ~ 2, mainly manifested by an increase in the Cu_0.02 fraction. At the annual timescale (2004), this internal Cu reactivity increased Cu_0.02 fluxes in the Garonne Branch by ~ 20% (3.6 t year⁻¹), with the equivalent of ~ 2.9 t year⁻¹ derived from the Cu_P fraction and ~ 0.7 t year⁻¹ from the colloidal (0.02-0.2 μm) fraction, without involving and/or affecting the Cu_C18 (hydrophobic metal-organic complexes) fraction.Combining data on Cu speciation with the results obtained by several independent techniques (DOC and POC measurements, 3D-fluorescence, and TEM) suggested close relationships between Cu behavior and OM transformation/restructuration along the turbidity gradient in the Garonne Branch. The observed Cu_0.02 addition was related to increasing humification (humification index HIX increased from 9 to 12, network formation) and labile OM degradation (Iγ/Iα ratio decreased from 0.70 to 0.44), going along with decreasing DOC and POC concentrations. Mass-balances suggest that in the studied system, degradation of OM may account for the release of ~ 25 μmol potentially bioaccessible Cu_0.02 per mole of particulate organic carbon mineralized.