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.     

Field evidence for copper mobilization by dissolved organic matter

Fluxes of copper from the sediments to the water column in response to the presence of dissolved organic matter were measured in field enclosures placed on the floor of the Contrary Creek arm of Lake Anna, Virginia. Experimental chambers received a spike input of either sodium humate or phytoplankton; unamended chambers served as controls. Over the subsequent five days, water samples were withdrawn from the chambers and analyzed for total and dissolved copper, total and dissolved organic carbon (DOC) Eh, pH, dissolved oxygen, dissolved sulfides and heterotrophic microbial activity. Chambers amended with phytoplankton did not experience a rise in dissolved copper concentrations. Furthermore, the concentrations of dissolved copper in these chambers were not well-correlated with DOC concentrations (r = 0.1175, P = 0.642). Dissolved copper concentrations in chambers amended with sodium humate rose approximately 500% and remained elevated for the duration of the experimental trial (5 days). In this treatment, dissolved copper concentrations were well-correlated with DOC concentrations (r = 0.798, P < 0.005). The increase in dissolved copper in the chambers amended with sodium humate was observed to persist despite reducing conditions which were confirmed by redox measurements and the occurrence of dissolved sulfides. The addition of sodium humate to the chamber water resulted in a net mobilization of copper to the water column from the sediments. In contrast, dissolved organic carbon generated by the decomposition of phytoplankton did not appear to mobilize copper over the time interval examined. None of the changes in soluble copper concentrations could be related to Eh or pH effects. Supplementary laboratory experiments corroborated the field trials. The results suggest that long term (but not short term) products of decomposition processes may enhance the concentration of dissolved copper in the water column by the formation of soluble organometallic complexes.     

Organic matter transport and degradation in the river Seine (France) after a combined sewer overflow

The impact of a combined sewer overflow (CSO) upon receiving waters has been studied in the river Seine during Summers 1995 and 1996. Three main events have been monitored with special attention paid to the computation of oxygen, carbon and suspended solids budgets. Bacterial biomass and bacterial production rates have been measured to provide a more accurate understanding of the carbon cycle of the river Seine. Oxygen consumption inside the polluted water masses was totally due to the activity of large bacteria discharged into the river by the CSO, the activity of native small bacteria did not significantly increase after CSOs. Suspended solids issued from the CSO very quickly settles in this deep, slowly flowing river. However, discharged dissolved organic carbon (DOC) cannot account for the observed oxygen depletions, the additional carbon source could be phytoplankton or deflocculated/degraded particulate organic matter.     

Effects of pulp and paper mill effluents on the microplankton and microbial self-purification capabilities of the Biobío River, Chile

Most studies focus on the ecotoxicity of pulp and paper mill effluents, rather than on how they affect the physicochemical and biological structure and the intrinsic ecological capabilities of the receiving watercourses. We investigated the impact of such effluents on the water quality, microplankton system and microbial self-purification capacity (degradation of polymeric organic compounds via extracellular enzymes) of the Biobío River in Chile. The physicochemical impact on the water quality was indicated by raised conductivity, by the pollution of the water body with nitrate, nitrite and soluble reactive phosphorus, by the appearance of tannin and lignin, and by the steady accumulation of inorganic and organic suspended matter (SPM) along the river. From the biological structure of the microplankton system, very low and declining concentrations of chlorophyll a and heterotrophic flagellate densities were determined. The pulp and paper mill effluents introduced high bacterial abundances and biomass concentrations into the river water. This reflects the effective use made of the abundantly available inorganic and organic nutrients within this industrial and municipal process water by bacteria adapted to these extreme environments, additionally supported by concomitant low grazing pressure derivable from low heterotrophic flagellate abundances. Indeed, in one section of the river affected by a pulp mill, the plant was found to significantly contribute to the self-cleaning capacity of the river. However, this elevated degradation capacity was not enough to compensate for the additionally discharged organic material which, together with the toxic effects of the paper plant effluents, significantly interferes with the ecological status of the Biobío River.     

Spring bloom in a hypereutrophic lake, lake Kasumigaura, Japan—III Phytoplankton abundance in standing stock of organic matter in lake water

The rapid increase of phytoplankton biomass was the major process for the increase of particulate organic matter in Lake Kasumigaura in 1980. During the first phytoplankton pulse in the bloom relative abundance of each component of organic matter in the lake water was: dissolved organic matter 100, phytoplankton 28, bacteria 27, and detrital particle 27. This relative abundance was maintained as a steady-state oscillation throughout the spring bloom similar to that usually observed in moderately eutrophic waters. Thus phytoplankton abundance in the standing stock of organic matter of the hypereutrophic water during the spring bloom does not show any marked difference from that of moderately eutrophic waters.     

Export of mercury downstream from reservoirs

Environmental effects monitoring at the La Grande hydroelectric complex (Québec, Canada) revealed important increases in mercury levels in fish caught downstream from reservoirs. A study was carried out in 1997 immediately below the Caniapiscau Reservoir to identify by which components mercury is transported downstream from reservoirs and to assess the amount of mercury being exported. Stomach contents of lake whitefish (Coregonus clupeaformis) captured immediately below the Caniapiscau Reservoir were examined to determine which components transfer mercury from lower trophic levels to fish. The analyses of water samples and drifting organisms collected below the reservoir indicate that the dissolved fraction (< 0.45 microm) and the suspended particulate matter (0.45-50 microm) are the major components by which methylmercury is transferred downstream of reservoirs, accounting for 64 and 33%, respectively, of the total amounts exported. Drifting organisms such as plant debris, benthic invertebrates, fish, phytoplankton and zooplankton are much less important pathways for mercury export because of their very low biomass per water volume coming out of the generating station, as opposed to the high biomass of suspended particulate matter. However, zooplankton is the major component by which methylmercury is directly transferred to non-piscivorous fish downstream.     

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.     

Influence of a stormwater sediment deposit on microbial and biogeochemical processes in infiltration porous media

The purpose of this study was to test the relative influence of organic matter quantity and quality and the pollutant content of a stormwater sediment deposit on mineralization processes, microbial characteristics, and the release of solutes in infiltration sediment systems. In microcosm experiments, two other natural sediment deposits (one low and one rich particulate organic matter deposits) were studied to compare their effects with those of the stormwater deposit. The results showed that the biogeochemical processes (aerobic respiration, denitrification, fermentative processes), the microbial metabolism (enzymatic activities), and the releases of several solutes (NH(4)(+) and DOC) were stimulated in presence of the stormwater deposit and the natural particulate organic matter (POM)-rich deposit because of the quantity of the POM in these deposits. In the stormwater deposit, the high availability of the POM (indicated by its low C/N ratio and its high P content) produced a higher stimulation of the microbial metabolism than in presence of the POM-rich deposit (with a high C/N ratio). Pollutant (hydrocarbon and heavy metal) contents of the stormwater deposit did not have a significant effect on microbial processes. Thus, main effects of the stormwater sedimentary deposit on infiltration system were due to its organic matter characteristics (quantity and quality). Such organic matter characteristics need to be considered in future studies to determine the contamination potential of stormwater management practices.     

Composition of particulate and dissolved organic matter in a disturbed watershed of southeast Brazil (Piracicaba River basin)

The elemental and isotopic composition of particulate and dissolved organic matter was investigated in the Piracicaba River basin, S?o Paulo State, Brazil. Comparison of riverine organic matter from the Piracicaba River basin, a region where rivers and streams receive urban sewage and industrial effluents, with data reported for the pristine Amazon system revealed significant differences associated with anthropogenic impacts. One important difference was N enrichment in the particulate organic material of the Piracicaba basin rivers, due to (a) urban and industrial effluents, and (b) enhanced phytoplankton growth, which results from the combination of nutrient enrichment and damming of sections of the rivers. Radiocarbon concentrations were overall more depleted (older 14C age) in the Piracicaba basin rivers than in the Amazon, which may reflect the importance of soil erosion in the former. Analyses of stable and radioactive carbon isotopes and lignin-derived compounds indicated that coarse particulate organic material is composed of a mixture of soil particles and degraded organic matter from C3 and C4 vascular plants. Fine particulate organic material was composed mainly of soil particles and phytoplankton cell remains, the latter especially during low water. Ultrafiltered dissolved organic matter was the most degraded fraction according to its lignin oxidation products, and showed the greatest influence of C4 plant sources.     

Microbially available organic carbon, phosphorus, and microbial growth in ozonated drinking water

Ozonation is a disinfection technique commonly used in the treatment of drinking water. It destroys harmful microbes, but it also degrades organic matter in water, increasing the bioavailability of organic matter. Recently, it was found that not only organic carbon but also phosphorus can limit the microbial growth in drinking water, which contains high amount of organic matter. We used a bioassay to analyze whether ozone could also increase the microbially available phosphorus (MAP) in drinking water, and whether MAP in ozone-treated water was associated with the growth of heterotrophic microbes. We found that both assimilable organic carbon and MAP concentrations were increased by ozone treatment. In ozonated water, microbial growth was mainly limited by phosphorus, and even minor changes in MAP concentration dramatically increased the growth potential of heterotrophic microbes. In this study, ozonation increased the MAP by 0.08-0.73 microgram P/l, resulting in an increase of 80,000-730,000 CFU/ml in water samples. In contrast to MAP, the content of assimilable organic carbon (AOCpotential) did not correlate with microbial growth. The results show that in water treatment not only AOCpotential but also MAP should be considered as an important factor that can limit microbial growth in drinking water.     

Measurement of streamwater biodegradable dissolved organic carbon with a plug-flow bioreactor

Plug-flow biofilm reactors were colonized by microorganisms indigenous to streamwater and used to measure concentrations of biodegradable dissolved organic carbon (DOC) in streamwater. We performed experiments to determine the influence of physical, chemical, and biological factors on the operation of the bioreactors. Colonization required several months and the biological removal of DOC within the reactors was influenced by hydraulic residence time, dissolved organic carbon concentration, and water temperature. The large microbial biomass within a bioreactor buffered bioreactor performance from changes in chemical and physical parameters.     

The effects of variability in the inherent optical properties on estimations of chlorophyll a by remote sensing in Swedish freshwaters

During late summer of 1997 measurements were made of the inherent optical properties in Lake M?laren, Sweden. These included measurements of the total particulate absorption, phytoplankton absorption, yellow substance absorption and total backscattering. Measurements were also made of concentrations known to affect the inherent optical properties; chlorophyll a and suspended particulate organic and inorganic matter. At the same time measurements of underwater radiance reflectance were made. The above measurements were used to better define the relationships between the inherent optical properties and the concentrations affecting them. Correlation analyses were also made in order to study covariation of the concentrations of suspended and dissolved substances in the data set. These relationships were then used to better parameterize a semi-analytical model predicting remote sensing reflectance. Multivariate sensitivity analyses showed that large variations on the Rr(700-710)/Rr(678-685) ratio vs. chlorophyll concentrations could be expected in a heterogeneous environment such as Lake M?laren. This could lead to large errors in subsequent estimates of chlorophyll concentrations.     

Carbon cycling in a zero-discharge mariculture system

Interest in mariculture systems will rise in the near future due to the decreased ability of the ocean to supply the increasing demand for seafood. We present a trace study using stable carbon and nitrogen isotopes and chemical profiles of a zero-discharge mariculture system stocked with the gilthead seabream (Sparus aurata). Water quality maintenance in the system is based on two biofiltration steps. Firstly, an aerobic treatment step comprising a trickling filter in which ammonia is oxidized to nitrate. Secondly, an anaerobic step comprised of a digestion basin and a fluidized bed reactor where excess organic matter and nitrate are removed. Dissolved inorganic carbon and alkalinity values were higher in the anaerobic loop than in the aerobic loop, in agreement with the main biological processes taking place in the two treatment steps. The δ¹³C of the dissolved inorganic carbon (δ¹³C_DIC) was depleted in ¹³C in the anaerobic loop as compared to the aerobic loop by 2.5-3‰. This is in agreement with the higher dissolved inorganic carbon concentrations in the anaerobic loop and the low water retention time and the chemolithotrophic activity of the aerobic loop. The δ¹³C and δ¹⁵N of organic matter in the mariculture system indicated that fish fed solely on feed pellets. Compared to feed pellets and particulate organic matter, the sludge in the digestion basin was enriched in ¹⁵N while δ¹³C was not significantly different. This latter finding points to an intensive microbial degradation of the organic matter taking place in the anaerobic treatment step of the system.     

Treatment of a colored groundwater by ozone-biofiltration: pilot studies and modeling interpretation

Pilot studies investigated the fates of color, dissolved organic carbon (DOC), and biodegradable organic matter (BOM) by the tandem of ozone plus biofiltration for treating a source water having significant color (50 cu) and DOC (3.2 mg/l). Transferred ozone doses were from 1.0 to 1.8 g O3/g C. Rapid biofilters used sand, anthracite, or granular activated carbon as media with empty-bed contact time (EBCT) up to 9 min. The pilot studies demonstrated that ozonation plus biofiltration removed most color and substantial DOC, and increasing the transferred ozone dose enhanced the removals. For the highest ozone dose, removals were as high as 90% for color and 38% for DOC. While most of the color removal took place during ozonation, most DOC removal occurred in the biofilters, particularly when the ozone dose was high. Compared to sand and anthracite biofilters, the GAC biofilter gave the best performance for color and DOC removal, but some of this enhanced performance was caused by adsorption, since the GAC was virgin at the beginning of the pilot studies. Backwashing events had no noticeable impact of the performance of the biofilters. The Transient-State, Multiple-Species Biofilm Model (TSMSBM) was used to interpret the experimental results. Model simulations show that soluble microbial products, which comprised a significant part of the effluent BOM, offset the removal of original BOM, a factor that kept the removal of DOC relatively constant over the range of EBCTs of 3.5-9 min. Although improved biofilm retention, represented by a small detachment rate, allowed more total biofilm accumulation and greater removal of original BOM, it also caused more release of soluble microbial products and the build up of inert biomass in the biofilm. Backwashing had little impact on biofilter performance, because it did not remove more than 25% of the biofilm under any condition simulated.     

Determination of biodegradable dissolved organic carbon in waters: comparison of batch methods

An effect of different types of bacterial inocula upon the final biodegradable dissolved organic carbon (BDOC) result was investigated in samples of both low and high BDOC concentrations. Stream water and leaf leachate samples were incubated either with free, suspended bacteria or with bacteria attached to the stream sediment particles or attached to artificial substrata. The time course of dissolved organic carbon (DOC) decomposition was observed using absorbance analysis of DOC. BDOC determination by means of commonly used suspended bacteria as the inoculum made for an underestimation of BDOC between 5% and 25%, compared with attached bacterial community (biofilm). The reason for these findings could be the higher microbial diversity, higher metabolic activity of attached bacteria and abiotic adsorption of organic molecules to inorganic support and biofilm matrix surfaces. Adsorbed DOC is easily hydrolyzed and utilized by biofilm bacteria.     

Relationships between organic carbon and microbial components in a Tyrrhenian area (Isola del Giglio) affected by mucilages

The chemical and biological properties of the water column at a Tyrrhenian site (Isola del Giglio) were studied during a 3-year period. The results highlighted the oligotrophic features of the site, characterised by quite low concentrations of organic carbon (on average DOC 102 micromol/L and POC 9 micromol/L). Relevant bacterial biomass (on average 42.1 microg C/L) and a notable activity (in terms of frequency of dividing cells, on average more than 5%) were observed. However, remarkable changes for these parameters were seasonally recorded. The cyclic occurrence, generally during the late spring-summer period, of benthic mucilage indicated that localised distrophic processes may occur. In particular, the benthic mucilage events of 2000 and 2001 were investigated, although some comparative information was available also for 1999 and 2002. The mucilage aggregates generally showed high bacterial colonisation, which have remarkable effects on the organic matter cycle both inside the aggregates and in the surrounding seawater. During the benthic mucilage development, an increase of DOC and POC concentrations was observed (up to 129 and 18 micromol/L, respectively, in June 2000 and up to 145 and 10 micromol/L, respectively, in May and June 2001) in the water column adjacent to the bottom. However, a general decrease of the trophic value of particulate matter (in terms of C/N ratio) was also observed, especially in 2000 after the disappearance of the mucilage. The available energy and organic matter during the mucilage events led to an increased presence of bacteria in the bottom waters of the Isola del Giglio, with maximum biomass values in 2001. Similarly, the replicative activity of bacteria was higher in 2001 (frequency of dividing cells about 5% vs. 3% of 2000). The lower activity of 2000, in addition to the lower trophic value of organic matter and different environmental conditions (namely lower temperature), might be involved in the persistence of mucilage in 2000 with respect to the rapid disappearance observed in 2001.     

Characteristics of dissolved organic matter following 20 years of peatland restoration

The changes in the amounts and composition of dissolved organic matter (DOM) following long-term peat restoration are unknown, although this fraction of soil organic matter affects many processes in such ecosystems. We addressed this lack of knowledge by investigating a peatland in south-west Germany that was partly rewetted 20 years ago. A successfully restored site and a moderately drained site were compared, where the mean groundwater levels were close to the soil surface and around 30 cm below surface, respectively. The concentrations of dissolved organic carbon (DOC) at 4 depths were measured over one year. The specific absorbance was measured at 280 nm and the fluorescence spectra were used to describe the aromaticity and complexity of DOM.The investigations showed that 20 years of peatland restoration was able to create typical peatland conditions. The rewetted site had significantly lower DOC concentrations at different depths compared to the drained site. The specific UV absorbance showed that the rewetted site had a lower level of aromatic DOM structures. The decreasing specific UV absorbance might indicate an increasing contribution of small organic molecules to DOM. It was hypothesized that the decreasing DOC concentrations and the relative enrichment of small, readily degradable organic molecules, reflect the slower decomposition of organic matter after the re-establishment of the water table. Seasonal trends provided substantial evidence for our hypothesis that reduced DOC concentrations were caused by reduced peat decomposition. During summer, the elevated DOC values were accompanied by an increase in DOM aromaticity and complexity. Our results demonstrated a close link between C mineralization and DOC production. We concluded that long-term peatland restoration in the form of the successful re-establishment of the water table might result in reduced peat decomposition and lower DOC concentrations. The restoration of peatlands seems to have a positive impact on C sequestration.     

Seawater quality and microbial communities at a desalination plant marine outfall. A field study at the Israeli Mediterranean coast

Global desalination quadrupled in the last 15 years and the relative importance of seawater desalination by reverse osmosis (SWRO) increased as well. While the technological aspects of SWRO plants are extensively described, studies on the environmental impact of brine discharge are lacking, in particular in situ marine environmental studies. The Ashqelon SWRO plant (333,000 m³ d⁻¹ freshwater) discharges brine and backwash of the pre-treatment filters (containing ferric hydroxide coagulant) at the seashore, next to the cooling waters of a power plant. At the time of this study brine and cooling waters were discharged continuously and the backwash discharge was pulsed, with a frequency dependent on water quality at the intake. The effects of the discharges on water quality and neritic microbial community were identified, quantified and attributed to the different discharges. The mixed brine-cooling waters discharge increased salinity and temperature at the outfall, were positively buoyant, and dispersed at the surface up to 1340 m south of the outfall. Nutrient concentrations were higher at the outfall while phytoplankton densities were lower. Chlorophyll-a and picophytoplankton cell numbers were negatively correlated with salinity, but more significantly with temperature probably as a result of thermal pollution. The discharge of the pulsed backwash increased turbidity, suspended particulate matter and particulate iron and decreased phytoplankton growth efficiency at the outfall, effects that declined with distance from the outfall. The discharges clearly reduced primary production but we could not attribute the effect to a specific component of the discharge. Bacterial production was also affected but differently in the three surveys. The combined and possible synergistic effects of SWRO desalination along the Israeli shoreline should be taken into account when the three existing plants and additional ones are expected to produce 2 Mm³ d⁻¹ freshwater by 2020.     

Biogeochemical behavior of organic carbon in the Trinity River downstream of a large reservoir lake in Texas, USA

Dissolved and particulate organic carbon concentrations were measured and annual loads estimated for the Trinity River, the main freshwater input source to Galveston Bay, which lies on the upper Gulf coast of Texas, USA, during 2000-2001. This river drains the forested lowlands south of a relatively large reservoir lake, Lake Livingston. A weak relationship between dissolved organic carbon (DOC) and Q(TR) indicated hydrologic control but separation of the data, based on individual discharge events, was necessary to improve interpretation. For instance, the first rain of the season resulted in only a modest increase in DOC concentrations and led to an inverse relationship with discharge, due to decreased lateral flow and increased infiltration of rainwater, with the lower flows being more efficient at DOC leaching from soils. In contrast, a long duration high discharge river crest event resulted in an opposite trend, i.e. a linear increase in DOC with increasing discharge rates. A short duration high discharge tropical storm showed reduced Trinity River DOC concentrations and the highest POC concentrations measured, likely resulting from the relatively short duration, and minimal contact time, of this event. In contrast to DOC, the concentrations of particulate organic carbon, POC (mg C l(-1)) were linearly correlated to suspended particulate matter (SPM) concentrations and accounted for between 10 and 12% of the total suspended load at low discharge but decreased to approximately 2% at high discharge. This suggests dilution by larger particles with a reduced organic carbon content, possibly silicate minerals, more readily resuspended at elevated levels of discharge. The annual total organic carbon (TOC) load to Galveston Bay, estimated from the slope of the daily load vs. discharge relationship, was 11.2 x 10(10) g C and calculated export coefficients (g C m(-2) year(-1)) were in good agreement with previous results. Using this relationship, accurate assessments of TOC flux inputs to Galveston Bay over the past quarter-century and in the future are possible by obtaining annual Trinity River discharge rates, which are readily available from the USGS. Comparing DOC riverine inputs to benthic sources in Trinity Bay, measured directly on the same day, indicates that the sediments contribute approximately 20% of total inputs of DOC to Trinity Bay. However, assuming a constant benthic source during low-flow conditions, which can occur for periods of up to 14 months in this region of Texas, benthic fluxes would account for > 80% of the total inputs into Trinity Bay. At high levels of discharge, the Trinity River discharges approximately 1.0 x 10(9) g C day(-1) and dominates DOC inputs to Trinity Bay.     

Buffering of recovery from acidification by organic acids

In the United Kingdom, as in other regions of Europe and North America, recent decreases in surface water sulphate concentrations, due to reduced sulphur emissions, have coincided with marked increases in dissolved organic carbon (DOC) concentrations. Since many of the compounds comprising DOC are acidic, the resulting increases in organic acidity may have the potential to offset the benefits of a decrease in mineral (sulphate) acidity. To test this, we used a triprotic model of organic acid dissociation to estimate the proportional organic acid buffering of reduced mineral acidity as measured in the 22 lakes and streams monitored by the UK Acid Waters Monitoring Network. For an average non-marine sulphate decrease of 30 mueq l(-1) over 15 years from 1988-2003, we estimate that around 28% was counterbalanced by rising strong organic acids, 20% by rising alkalinity (partly attributable to an increase in weak organic acids), 11% by falling inorganic aluminium and 41% by falling non-marine base cations. The situation is complicated by a concurrent decrease in marine ion concentrations, and the impact this may have had on both DOC and acidity, but results clearly demonstrate that organic acid increases have substantially limited the amount of recovery from acidification (in terms of rising alkalinity and falling aluminium) that have resulted from reducing sulphur emissions. The consistency and magnitude of sulphate and organic acid changes are consistent with a causal link between the two, possibly due to the effects of changing acidity, ionic strength and aluminium concentrations on organic matter solubility. If this is the case, then organic acids can be considered effective but partial buffers to acidity change in organic soils, and this mechanism needs to be considered in assessing and modelling recovery from acidification, and in defining realistic reference conditions. However, large spatial variations in the relative magnitude of organic acid and sulphate changes, notably for low-deposition sites in northwestern areas where organic acid increases apparently exceed non-marine sulphate decreases, suggest that additional factors, such as changes in sea-salt deposition and climatic factors, may be required to explain the full magnitude of DOC increases in UK surface waters.