Have increased dissolved organic carbon (DOC) losses from UK peat and organo-mineral soils been driven by the decline in acid rain?

Dissolved organic carbon (DOC) concentrations have been rising in streams and lakes draining catchments with organic soils across Northern Europe. These increases have shown a correlation with decreased sulphate and chloride concentrations. One hypothesis to explain this phenomenon is that these relationships are due an increased in DOC release from soils to freshwaters, caused by a decline in pollutant sulphur and sea-salt deposition. We carried out controlled deposition experiments in the laboratory on intact peat and organomineral O-horizon cores to test this hypothesis. Preliminary data showed a clear correlation between the change in soil water pH and change in DOC concentrations, however uncertainty still remains about whether this is due to changes in biological activity or chemical solubility.

Dissolved organic carbon (DOC) in Arctic ground ice, from northwest Canada, east Siberia, and Alaska

Thermal permafrost degradation and coastal erosion in the Arctic remobilize substantial amounts of organic carbon (OC) and nutrients which have accumulated in late Pleistocene and Holocene unconsolidated deposits. Permafrost vulnerability to thaw subsidence, collapsing coastlines and irreversible landscape change are largely due to the presence of large amounts of massive ground ice such as ice wedges. However, ground ice has not, until now, been considered to be a source of dissolved organic carbon (DOC), dissolved inorganic carbon (DIC) and other elements which are important for ecosystems and carbon cycling. Here we show, using biogeochemical data from a large number of different ice bodies throughout the Arctic, that ice wedges have the greatest potential for DOC storage, with a maximum of 28.6 mg/L (mean: 9.6 mg/L). Variation in DOC concentration is positively correlated with and explained by the concentrations and relative amounts of typically terrestrial cations such as Mg2+ and K+. DOC sequestration into ground ice was more effective during the late Pleistocene than during the Holocene, which can be explained by rapid sediment and OC accumulation, the prevalence of more easily degradable vegetation and immediate incorporation into permafrost. We assume that pristine snowmelt is able to leach considerable amounts of well-preserved and highly bioavailable DOC as well as other elements from surface sediments, which are rapidly frozen and stored in ground ice, especially in ice wedges, even before further degradation. We found that ice wedges in the Yedoma region represent a significant DOC (45.2 Tg) and DIC (33.6 Tg) pool in permafrost areas and a freshwater reservoir of 4200 km**3. This study underlines the need to discriminate between particulate OC and DOC to assess the availability and vulnerability of the permafrost carbon pool for ecosystems and climate feedback upon mobilization.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, Ross Sea

Dissolved and particulate organic matter was measured during six cruises to the southern Ross Sea. The cruises were conducted during late austral winter to autumn from 1994 to 1997 and included coverage of various stages of the seasonal phytoplankton bloom. The data from the various years are compiled into a representative seasonal cycle in order to assess general patterns of dissolved organic matter (DOM) and particulate organic matter (POM) dynamics in the southern Ross Sea. Dissolved organic carbon (DOC) and particulate organic carbon (POC) were at background concentrations of approximately 42 and 3 µM C, respectively, during the late winter conditions in October. As the spring phytoplankton bloom progressed, organic matter increased, and by January DOC and POC reached as high as 30 and 107 µM C, respectively, in excess of initial wintertime conditions. Stocks and concentrations of DOC and POC returned to near background values by autumn (April). Approximately 90% of the accumulated organic matter was partitioned into POM, with modest net accumulation of DOM stocks despite large net organic matter production and the dominance of Phaeocystis antarctica. Changes in NO3 concentration from wintertime values were used to calculate the equivalent biological drawdown of dissolved inorganic carbon (DICequiv). The fraction of DICequiv drawdown resulting in net DOC production was relatively constant (ca. 11%), despite large temporal and spatial variability in DICequiv drawdown. The C : N (molar ratio) of the seasonally produced DOM had a geometric mean of 6.2 and was nitrogen-rich compared to background DOM. The DOM stocks that accumulate in excess of deep refractory background stocks are often referred to as "semi-labile" DOM. The "semi-labile" pool in the Ross Sea turns over on timescales of about 6 months. As a result of the modest net DOM production and its lability, the role DOM plays in export to the deep sea is small in this region.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, Southern Ocean

Recent evidence that dissolved organic carbon (DOC) is a significant component of the organic carbon flux below the photic layer of the ocean (1), together with verification of high respiration rates in the dark ocean (2), suggests that the downward flux of DOC may play a major role in supporting respiration there. Here we show, on the basis of examination of the relation between DOC and apparent oxygen utilization (AOU), that the DOC flux supports ~10% of the respiration in the dark ocean. The contribution of DOC to pelagic respiration below the surface mixed layer can be inferred from the relation between DOC and apparent oxygen utilization (AOU, µM O2), a variable quantifying the cumulative oxygen consumption since a water parcel was last in contact with the atmosphere. However, assessments of DOC/AOU relations have been limited to specific regions of the ocean (3, 4) and have not considered the global ocean. We assembled a large data set (N = 9824) of concurrent DOC and AOU observations collected in cruises conducted throughout the world's oceans (fig. S1, table S1) to examine the relative contribution of DOC to AOU and, therefore, respiration in the dark ocean. AOU increased from an average (±SE) 96.3 ± 2.0 µM at the base of the surface mixed layer (100 m) to 165.5 ± 4.3 µM at the bottom of the main thermocline (1000 m), with a parallel decline in the average DOC from 53.5 ± 0.2 to 43.4 ± 0.3 µM C (Fig. 1). In contrast, there is no significant decline in DOC with increasing depth beyond 1000 m depth (Fig. 1), indicating that DOC exported with overturning circulation plays a minor role in supporting respiration in the ocean interior (5). Assuming a molar respiratory quotient of 0.69, the decline in DOC accounts for 19.6 ± 0.4% of the AOU within the top 1000 m (Fig. 1). This estimate represents, however, an upper limit, because the correlation between DOC and AOU is partly due to mixing of DOC-rich warm surface waters with DOC-poor cold thermocline waters (6). Removal of this effect by regressing DOC against AOU and water temperature indicates that DOC supports only 8.4 ± 0.3% of the respiration in the mesopelagic waters.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, Azores-I

Temperate, transitional and subtropical waters of the remote Azores Front region east of Azores (24-40°N, 22-32°W) were sampled during three cruises conducted under increasing stratification conditions (April 1999, May 1997 and August 1998). Despite the temporal increase of surface temperature (by 5 °C) and stratification (by 2.1 1/min**2), as well as the thermocline shoaling (by ~15 m), dissolved organic carbon (DOC) and nitrogen (DON) in the surface layer were not significantly different for the early spring, late spring and summer periods, with average concentrations of 69±2 µM-C and 5.2±0.4 µM-N, respectively. The surface excess of semi-labile DOC, compared with the baseline DOC concentration in the deep ocean (47±2 µM-C), represents 33% of the bulk DOC concentration and as much as 85% of the TOC (=POC+DOC) excess. When compared with the winter baseline (56±2 µM-C), the seasonal surface DOC excess is 20% of the bulk DOC concentration and 87% of the seasonal TOC excess. These results confirm the major role played by DOC in the carbon cycle of surface waters of the Azores Front region. The total amount of bioreactive DOC transported from the temperate to the subtropical North Atlantic by the Ekman flux between March and December represents only ~15% of the average annual primary production, and ~15% and ~30% of the measured sinking POC flux+vertical DOC eddy diffusion during early spring and summer, respectively. Vertical eddy diffusion is 35% and 2% of the spring and summer sinking POC flux, respectively. On the other hand, DOC only contributes 13% to the local oxidation of organic matter in subsurface waters (between the pycnocline and 500 m) of the study region.

Modeling the mechanisms that control in-stream dissolved organic carbon dynamics in upland and forested catchments

[1] We present a new, process-based model of soil and stream water dissolved organic carbon (DOC): the Integrated Catchments Model for Carbon (INCA-C). INCA-C is the first model of DOC cycling to explicitly include effects of different land cover types, hydrological flow paths, in-soil carbon biogeochemistry, and surface water processes on in-stream DOC concentrations. It can be calibrated using only routinely available monitoring data. INCA-C simulates daily DOC concentrations over a period of years to decades. Sources, sinks, and transformation of solid and dissolved organic carbon in peat and forest soils, wetlands, and streams as well as organic carbon mineralization in stream waters are modeled. INCA-C is designed to be applied to natural and seminatural forested and peat-dominated catchments in boreal and temperate regions. Simulations at two forested catchments showed that seasonal and interannual patterns of DOC concentration could be modeled using climate-related parameters alone. A sensitivity analysis showed that model predictions were dependent on the mass of organic carbon in the soil and that in-soil process rates were dependent on soil moisture status. Sensitive rate coefficients in the model included those for organic carbon sorption and desorption and DOC mineralization in the soil. The model was also sensitive to the amount of litter fall. Our results show the importance of climate variability in controlling surface water DOC concentrations and suggest the need for further research on the mechanisms controlling production and consumption of DOC in soils.

Utilizing chromophoric dissolved organic matter measurements to derive export and reactivity of dissolved organic carbon exported to the Arctic Ocean: A case study of the Yukon River, Alaska

The quality and quantity of dissolved organic matter (DOM) exported by Arctic rivers is known to vary with hydrology and this exported material plays a fundamental role in the biogeochemical cycling of carbon at high latitudes. We highlight the potential of optical measurements to examine DOM quality across the hydrograph in Arctic rivers. Furthermore, we establish chromophoric DOM (CDOM) relationships to dissolved organic carbon (DOC) and lignin phenols in the Yukon River and model DOC and lignin loads from CDOM measurements, the former in excellent agreement with long-term DOC monitoring data. Intensive sampling across the historically under-sampled spring flush period highlights the importance of this time for total export of DOC and particularly lignin. Calculated riverine DOC loads to the Arctic Ocean show an increase from previous estimates, especially when new higher discharge data are incorporated. Increased DOC loads indicate decreased residence times for terrigenous DOM in the Arctic Ocean with important implications for the reactivity and export of this material to the Atlantic Ocean.

Alternative explanations for rising dissolved organic carbon export from organic soils

Since 1988, there has been, on average, a 91% increase in dissolved organic carbon (DOC) concentrations of UK lakes and streams in the Acid Waters Monitoring Network (AWMN). Similar DOC increases have been observed in surface waters across much of Europe and North America. Much of the debate about the causes of rising DOC has, as in other studies relating to the carbon cycle, focused on factors related to climate change. Data from our peat-core experiments support an influence of climate on DOC, notably an increase in production with temperature under aerobic, and to a lesser extent anaerobic, conditions. However, we argue that climatic factors may not be the dominant drivers of DOC change. DOC solubility is suppressed by high soil water acidity and ionic strength, both of which have decreased as a result of declining sulphur deposition since the 1980s, augmented during the 1990s in the United Kingdom by a cyclical decline in sea-salt deposition. Our observational and experimental data demonstrate a clear, inverse and quantitatively important link between DOC and sulphate concentrations in soil solution. Statistical analysis of 11 AWMN lakes suggests that rising temperature, declining sulphur deposition and changing sea-salt loading can account for the majority of the observed DOC trend. This combination of evidence points to the changing chemical composition of atmospheric deposition, particularly the substantial reduction in anthropogenic sulphur emissions during the last 20 years, as a key cause of rising DOC. The implications of rising DOC export for the carbon cycle will be very different if linked primarily to decreasing acid deposition, rather than to changes in climate, suggesting that these systems may be recovering rather than destabilising.

Export of dissolved organic carbon from an upland peatland during storm events: implications for flux estimates

Most of the dissolved organic carbon (DOC) exported from catchments is transported during storm events. Accurate assessments of DOC fluxes are essential to understand long-term trends in the transport of DOC from terrestrial to aquatic systems, and also the loss of carbon from peatlands to determine changes in the source/sink status of peatland carbon stores. However, many long-term monitoring programmes collect water samples at a frequency (e.g. weekly/monthly) less than the time period of a typical storm event (typically <1–2 days). As widespread observations in catchments dominated by organo-mineral soils have shown that both concentration and flux of DOC increases during storm events, lower frequency monitoring could result in substantial underestimation of DOC flux as the most dynamic periods of transport are missed. However, our intensive monitoring study in a UK upland peatland catchment showed a contrasting response to these previous studies. Our results showed that (i) DOC concentrations decreased during autumn storm events and showed a poor relationship with flow during other seasons; and that (ii) this decrease in concentrations during autumn storms caused DOC flux estimates based on weekly monitoring data to be over-estimated, rather than under-estimated, because of over rather than under estimation of the flow-weighted mean concentration used in flux calculations. However, as DOC flux is ultimately controlled by discharge volume, and therefore rainfall, and the magnitude of change in discharge was greater than the magnitude of decline in concentrations, DOC flux increased during individual storm events. The implications for long-term DOC trends are therefore contradictory, as increased rainfall could increase flux but cause an overall decrease in DOC concentrations from peatland streams. Care needs to be taken when interpreting long-term trends in DOC flux rather than concentration; as flux is calculated from discharge estimates, and discharge is controlled by rainfall, DOC flux and rainfall/discharge will always be well correlated.

Influence of drought-induced acidification on the mobility of dissolved organic carbon in peat soils

A strong relationship between dissolved organic carbon (DOC) and sulphate (SO42−) dynamics under drought conditions has been revealed from analysis of a 10-year time series (1993–2002). Soil solution from a blanket peat at 10 cm depth and stream water were collected at biweekly and weekly intervals, respectively, by the Environmental Change Network at Moor House-Upper Teesdale National Nature Reserve in the North Pennine uplands of Britain. DOC concentrations in soil solution and stream water were closely coupled, displaying a strong seasonal cycle with lowest concentrations in early spring and highest in late summer/early autumn. Soil solution DOC correlated strongly with seasonal variations in soil temperature at the same depth 4-weeks prior to sampling. Deviation from this relationship was seen, however, in years with significant water table drawdown (>−25 cm), such that DOC concentrations were up to 60% lower than expected. Periods of drought also resulted in the release of SO42−, because of the oxidation of inorganic/organic sulphur stored in the peat, which was accompanied by a decrease in pH and increase in ionic strength. As both pH and ionic strength are known to control the solubility of DOC, inclusion of a function to account for DOC suppression because of drought-induced acidification accounted for more of the variability of DOC in soil solution (R2=0.81) than temperature alone (R2=0.58). This statistical model of peat soil solution DOC at 10 cm depth was extended to reproduce 74% of the variation in stream DOC over this period. Analysis of annual budgets showed that the soil was the main source of SO42− during droughts, while atmospheric deposition was the main source in other years. Mass balance calculations also showed that most of the DOC originated from the peat. The DOC flux was also lower in the drought years of 1994 and 1995, reflecting low DOC concentrations in soil and stream water. The analysis presented in this paper suggests that lower concentrations of DOC in both soil and stream waters during drought years can be explained in terms of drought-induced acidification. As future climate change scenarios suggest an increase in the magnitude and frequency of drought events, these results imply potential for a related increase in DOC suppression by episodic acidification.

Acidity controls on dissolved organic carbon mobility in organic soils

Dissolved organic carbon (DOC) concentrations in surface waters have increased across much of Europe and North America, with implications for the terrestrial carbon balance, aquatic ecosystem functioning, water treatment costs and human health. Over the past decade, many hypotheses have been put forward to explain this phenomenon, from changing climate and land-management to eutrophication and acid deposition. Resolution of this debate has been hindered by a reliance on correlative analyses of time-series data, and a lack of robust experimental testing of proposed mechanisms. In a four-year, four-site replicated field experiment involving both acidifying and de-acidifying treatments, we tested the hypothesis that DOC leaching was previously suppressed by high levels of soil acidity in peat and organo-mineral soils, and therefore that observed DOC increases a consequence of decreasing soil acidity. We observed a consistent, positive relationship between DOC and acidity change at all sites. Responses were described by similar hyperbolic relationships between standardised changes in DOC and hydrogen ion concentrations at all sites, suggesting potentially general applicability. These relationships explained a substantial proportion of observed changes in peak DOC concentrations in nearby monitoring streams, and application to a UK-wide upland soil pH dataset suggests that recovery from acidification alone could have led to soil solution DOC increases in the range 46-126% by habitat type since 1978. Our findings raise the possibility that changing soil acidity may have wider impacts on ecosystem carbon balances. Decreasing sulphur deposition may be accelerating terrestrial carbon loss, and returning surface waters to a natural, high-DOC condition.

Assessment of potential climate change impacts on peatland dissolved organic carbon release and drinking water treatment from laboratory experiments

Catchments draining peat soils provide the majority of drinking water in the UK. Over the past decades, concentrations of dissolved organic carbon (DOC) have increased in surface waters. Residual DOC can cause harmful carcinogenic disinfection by-products to form during water treatment processes. Increased frequency and severity of droughts combined with and increased temperatures expected as the climate changes, have potentials to change water quality. We used a novel approach to investigate links between climate change, DOC release and subsequent effects on drinking water treatment. We designed a climate manipulation experiment to simulate projected climate changes and monitored releases from peat soil and litter, then simulated coagulation used in water treatment. We showed that the ‘drought’ simulation was the dominant factor altering DOC release and affected the ability to remove DOC. Our results imply that future short-term drought events could have a greater impact than increased temperature on DOC treatability.

Simulated climate change impact on summer dissolved organic carbon release from peat and surface vegetation: implications for drinking water treatment

Uncertainty regarding changes in dissolved organic carbon (DOC) quantity and quality has created interest in managing peatlands for their ecosystem services such as drinking water provision. The evidence base for such interventions is, however, sometimes contradictory. We performed a laboratory climate manipulation using a factorial design on two dominant peatland vegetation types (Calluna vulgaris and Sphagnum Spp.) and a peat soil collected from a drinking water catchment in Exmoor National Park, UK. Temperature and rainfall were set to represent baseline and future conditions under the UKCP09 2080s high emissions scenario for July and August. DOC leachate then underwent standard water treatment of coagulation/flocculation before chlorination. C. vulgaris leached more DOC than Sphagnum Spp. (7.17 versus 3.00 mg g−1) with higher specific ultraviolet (SUVA) values and a greater sensitivity to climate, leaching more DOC under simulated future conditions. The peat soil leached less DOC (0.37 mg g−1) than the vegetation and was less sensitive to climate. Differences in coagulation removal efficiency between the DOC sources appears to be driven by relative solubilisation of protein-like DOC, observed through the fluorescence peak C/T. Post-coagulation only differences between vegetation types were detected for the regulated disinfection by-products (DBPs), suggesting climate change influence at this scale can be removed via coagulation. Our results suggest current biodiversity restoration programmes to encourage Sphagnum Spp. will result in lower DOC concentrations and SUVA values, particularly with warmer and drier summers.

Fine-scale temporal characterization of trends in soil water dissolved organic carbon and potential drivers

Long-term monitoring of surface water quality has shown increasing concentrations of Dissolved Organic Carbon (DOC) across a large part of the Northern Hemisphere. Several drivers have been implicated including climate change, land management change, nitrogen and sulphur deposition and CO2 enrichment. Analysis of stream water data, supported by evidence from laboratory studies, indicates that an effect of declining sulphur deposition on catchment soil chemistry is likely to be the primary mechanism, but there are relatively few long term soil water chemistry records in the UK with which to investigate this, and other, hypotheses directly. In this paper, we assess temporal relationships between soil solution chemistry and parameters that have been argued to regulate DOC production and, using a unique set of co-located measurements of weather and bulk deposition and soil solution chemistry provided by the UK Environmental Change Network and the Intensive Forest Monitoring Level II Network . We used statistical non-linear trend analysis to investigate these relationships at 5 forested and 4 non-forested sites from 1993 to 2011. Most trends in soil solution DOC concentration were found to be non-linear. Significant increases in DOC occurred mostly prior to 2005. The magnitude and sign of the trends was associated qualitatively with changes in acid deposition, the presence/absence of a forest canopy, soil depth and soil properties. The strongest increases in DOC were seen in acidic forest soils and were most clearly linked to declining anthropogenic acid deposition, while DOC trends at some sites with westerly locations appeared to have been influenced by shorter-term hydrological variation. The results indicate that widespread DOC increases in surface waters observed elsewhere, are most likely dominated by enhanced mobilization of DOC in surficial organic horizons, rather than changes in the soil water chemistry of deeper horizons. While trends in DOC concentrations in surface horizons have flattened out in recent years, further increases may be expected as soil chemistry continues to adjust to declining inputs of acidity.