A brief overview of modern directions in marine DOC studies part I.--Methodological aspects

The necessity for determining the role of dissolved organic carbon (DOC) in the global carbon cycle stimulated the development of different methods of DOC analysis in aquatic environments. Progress in this direction has been made by oceanographers who developed and introduced a high-temperature catalytic oxidation (HTC) method for low organic carbon concentrations. Today this method is the reference method for marine DOC study. The combination of available reference materials and the participation in intercalibration exercises has resulted in both an increased accuracy and higher precision for this method. The HTC method completely oxidizes the more resistant DOC; makes information rapidly available following the completion of the field analysis; provides a high precision (down to 0.5 microM C); covers the range of seawater DOC concentrations (35-80 microM C and higher); with certain modifications it has proved to be both seaworthy and amenable to automated analysis; and the reliable and relatively easy to operate HTC analyzer is commercially available and easily combined with a total nitrogen analyzer for simultaneous measurements of both parameters in the same sample. In this review we summarize some aspects of sample collection, handling and the analytical chemistry of the DOC analysis by the HTC technique in marine study.     

Effects of wetland recovery on soil labile carbon and nitrogen in the Sanjiang Plain

Soil management significantly affects the soil labile organic factors. Understanding carbon and nitrogen dynamics is extremely helpful in conducting research on active carbon and nitrogen components for different kinds of soil management. In this paper, we examined the changes in microbial biomass carbon (MBC), microbial biomass nitrogen (MBN), dissolved organic carbon (DOC), and dissolved organic nitrogen (DON) to assess the effect and mechanisms of land types, organic input, soil respiration, microbial species, and vegetation recovery under Deyeuxia angustifolia freshwater marshes (DAMs) and recovered freshwater marsh (RFM) in the Sanjiang Plain, Northeast China. Identifying the relationship among the dynamics of labile carbon, nitrogen, and soil qualification mechanism using different land management practices is therefore important. Cultivation and land use affect intensely the DOC, DON, MBC, and MBN in the soil. After DAM soil tillage, the DOC, DON, MBC, and MBN at the surface of the agricultural soil layer declined significantly. In contrast, their recovery was significant in the RFM surface soil. A long time was needed for the concentration of cultivated soil total organic carbon and total nitrogen to be restored to the wetland level. The labile carbon and nitrogen fractions can reach a level similar to that of the wetland within a short time. Typical wetland ecosystem signs, such as vegetation, microbes, and animals, can be recovered by soil labile carbon and nitrogen fraction restoration. In this paper, the D. angustifolia biomass attained natural wetland level after 8 years, indicating that wetland soil labile fractions can support wetland eco-function in a short period of time (4 to 8 years) for reconstructed wetland under suitable environmental conditions.     

Study of the effect of pH, salinity and DOC on fluorescence of synthetic mixtures of freshwater and marine salts

In order to provide support for the discussion of the fate of organic matter in estuaries, a laboratory simulation was performed by changing freshwater ionic strength, pH and organic matter content. The change in spectroscopic characteristics caused by variations in salinity, pH and organic matter concentration in the filtered samples was observed by UV-Vis and fluorescence spectroscopy. The increase in emission fluorescence intensity of dissolved organic matter (DOM) due to increasing salinity (in the range 0 to 5 g l-1) is affected by the pH of the samples. The emission fluorescence intensity at the three maxima observed in the fluorescence spectra, is linearly correlated with dissolved organic carbon (DOC) concentration at several salinity values in the same sample. The increase in organic matter concentration caused a shift in the emission peak wavelength at 410 nm for several salinity values. We concluded that it is necessary to take into account the influence of salinity and pH on emission fluorescence of dissolved organic matter if it is to be used as a tracer in estuarine or near shore areas.     

CDOM fluorescence as a proxy of DOC concentration in natural waters: a comparison of four contrasting tropical systems

Chromophoric dissolved organic matter (CDOM) fluorescence or absorption is often proposed as a rapid alternative to chemical methods for the estimation of bulk dissolved organic carbon (DOC) concentration in natural waters. However, the robustness of this method across a wide range of systems remains to be shown. We measured CDOM fluorescence and DOC concentration in four tropical freshwater and coastal environments (estuary and coastal, tropical shallow lakes, water from the freshwater lens of two small islands, and soil leachates). We found that although this method can provide an estimation of DOC concentration in sites with low variability in DOC and CDOM sources in systems where the variability of DOC and CDOM sources are high, this method should not be used as it will lead to errors in the estimation of the bulk DOC concentration.     

Characterization of dissolved organic carbon at low levels in environmental waters by microfluidic-chip-based capillary gel electrophoresis with a laser-induced fluorescence detector

A microfluidic analytical system for characterization of dissolved organic carbon (DOC) in environmental waters, based on a capillary gel electrophoresis (CGE) device with a laser-induced fluorescence (LEF) detector, was developed. The applied voltage and the running buffer were investigated to control the simple floating injection and CGE separation for convenient cross-type microchips made from polymethylmethacylate. We obtained reproducible peaks for standard organic solutions and the determination time is less than 70 s. The values of the relative standard deviation (RSD) were 0.17–2.01% for repetitive injection (n?=?12). We demonstrated high-throughput characterization of DOC in environmental water from the Biwa Lake and the Hino River using microfluidic chip and determined that the content of DOC in the Biwa Lake changed with the seasons.     

Long-term changes in acidity and DOC in throughfall and soil water in Finnish forests

The main objective of this study was to examine if any detectable trends in dissolved organic carbon (DOC), sulphate (SO₄-S) concentrations and acid neutralizing capacity (ANC) in throughfall (TF) and soil water (SW) could be found during 1990–2010 and to relate them to recent changes in decreased acid deposition. The study was conducted in seven boreal coniferous forest sites: four of which are managed and three unmanaged forests sites. Generally, temporal trend showed a significant decrease in SO₄-S concentrations in bulk precipitation (BP), TF and SW. At some of the sites, there was an increasing tendency in BP and TF in the DOC concentrations. This feature coincides with decreasing SO₄-S concentration, indicating that SO₄-S may be an important driver of DOC release from the canopy. However, a slightly increased temperature, larger senescing needle mass and consequently increased decaying activity in the canopy may partly explain the increasing trend in DOC. In SW, no consistent DOC trend was seen. At some sites, the decreased base cation concentrations mostly account for the decrease in the ANC values in SW and TF.     

Longitudinal variability in streamwater chemistry and carbon and nitrogen fluxes in restored and degraded urban stream networks

Stream restoration has increasingly been used as a best management practice for improving water quality in urbanizing watersheds, yet few data exist to assess restoration effectiveness. This study examined the longitudinal patterns in carbon and nitrogen concentrations and mass balance in two restored (Minebank Run and Spring Branch) and two unrestored (Powder Mill Run and Dead Run) stream networks in Baltimore, Maryland, USA. Longitudinal synoptic sampling showed that there was considerable reach-scale variability in biogeochemistry (e.g., total dissolved nitrogen (TDN), dissolved organic carbon (DOC), cations, pH, oxidation/reduction potential, dissolved oxygen, and temperature). TDN concentrations were typically higher than DOC in restored streams, but the opposite pattern was observed in unrestored streams. Mass balances in restored stream networks showed net uptake of TDN across subreaches (mean ± standard error net uptake rate of TDN across sampling dates for Minebank Run and Spring Branch was 420.3 ± 312.2 and 821.8 ± 570.3 mg m(-2) d(-1), respectively). There was net release of DOC in the restored streams (1344 ± 1063 and 1017 ± 944.5 mg m(-2) d(-1) for Minebank Run and Spring Branch, respectively). Conversely, degraded streams, Powder Mill Run and Dead Run showed mean net release of TDN across sampling dates (629.2 ± 167.5 and 327.1 ± 134.5 mg m(-2) d(-1), respectively) and net uptake of DOC (1642 ± 505.0 and 233.7 ± 125.1 mg m(-2) d(-1), respectively). There can be substantial C and N transformations in stream networks with hydrologically connected floodplain and pond features. Assessment of restoration effectiveness depends strongly on where monitoring is conducted along the stream network. Monitoring beyond the stream-reach scale is recommended for a complete perspective of evaluation of biogeochemical function in restored and degraded urban streams.     

Mercury in rivers in NW England: from rural headwaters to the heartlands of the historic industrial base

Total mercury (T-Hg) concentrations in rivers are described across a rural to urban/industrial and agricultural landscape gradient in NW England. T-Hg ranges between 0.2 and 230 ng L(-1). The regional median was 3.6 ng L(-1) with individual river medians ranging between 1.9 and 8.3 ng L(-1). Median T-Hg concentrations were sometimes moderately higher for the lowland areas and at higher flows. Our estimates suggest that the Ribble estuary receives 9.2 kg y(-1) and the Wyre estuary 0.7 kg y(-1). In order to examine regional inputs from urban/industrial components, regression analysis was undertaken by comparing three types of hydrochemical signature: suspended sediments (SS), which provide a measure of the particulate component, dissolved organic carbon (DOC) that provides an indication of humic/fulvic acids that are part of the organic colloids and strong chelating agents, and boron a marker of sewage effluents and population density. The results show high positive relationships of T-Hg with both SS and DOC, but no relationship with the urban/industrial signal. The regression analysis with T-Hg indicated on average a gradient of 0.33 ng mg(-1) for DOC and 0.2 ng mg(-1) for SS. They indicate the primary importance of a diffuse source of T-Hg. For the upland areas and cleaner river systems, the linkages between T-Hg and DOC were particularly strong, while for the lowland areas, the linkage with SS proved stronger. Analysis of a latter subset of data that partition the SS into organic and inorganic fractions indicated that the T-Hg was primarily linked with the organic fraction. Indeed, multiple regression of T-Hg with DOC and POM reveals gradients similar to other parts of the World.     

Evaluating the Efficiency of Coagulation in the Removal of Dissolved Organic Carbon from Reservoir Water using Fluorescence and Ultraviolet Photometry

The present study used ultraviolet absorption (UVa) and the florescence intensity (FI) to evaluate the coagulation efficiency for removing dissolved organic carbon (DOC) in the raw water from Min-Ter, Li-Yu-Ten and Yun-Ho-Shen reservoirs in Taiwan. The results indicated that the ratio of DOC removal rate and FI removal rate was maintained at about 1 at various coagulant dosages. However, the ratio of DOC removal rate and UVa removal rate decreased as the coagulant dosage increased. In addition, after coagulation, the use of florescence intensity instead of total organic carbon (TOC) is better than UVa for measuring the DOC removal rate of the raw waters gathered in different months from the three reservoirs. Furthermore, a good linear relationship between florescence intensity and DOC removal rate was observed, and the DOC/FI ratio of raw water from each reservoir can be used to predict the DOC residual concentration after enhanced coagulation. This result shows that fluorescence analysis can be used for on-line and continuous monitoring the effectiveness of organic matter removal in water treatment.     

Reduction of dissolved organic matter in terms of DOC, UV-254, SUVA and THMFP in industrial estate wastewater treated by stabilization ponds

The aim of this research was to monitor the influent and effluent water quality of the aeration, facultative and oxidation water treatment ponds of an industrial estate. This industrial estate, the largest in northern Thailand, has proposed to utilization of reclaimed treated wastewater in their raw water supply so as to cope with the yearly water shortage during the dry season. Water samples were collected four times from four sampling points and evaluated for their dissolved organic matter (DOM) content in terms of dissolved organic carbon (DOC), ultraviolet light absorbance at 254 nm (UV-254), specific ultraviolet absorption (SUVA), trihalomethane formation potential (THMFP) and trihalomethane (THM) species. Average values of DOC, UV-254, SUVA and THMFP in the influent wastewater of 12.9 mg L⁻¹, 0.165 cm⁻¹, 1.29 L mg⁻¹m⁻¹ and 1.24 mg L⁻¹, respectively, were observed. The aeration ponds produced the best results: a 54% reduction of DOC, a 33% reduction of UV-254, and a 57% reduction of THMFP. However, SUVA in the aeration pond effluent showed a moderate increase. The facultative ponds and oxidation ponds did not take part in the reduction of DOC, UV-254, SUVA and THMFP. Average DOC, UV-254, SUVA and THMFP value of the treated wastewater were 5.8 mg L⁻¹, 0.107 cm⁻¹, 1.85 L mg⁻¹m⁻¹ and 468 μg L⁻¹, respectively. Chloroform, at 72.6% of total THMFP, was found to be the predominant THM species.     

Natural and Anthropogenic Factors Controlling the Dissolved Organic Carbon Concentrations and Fluxes in a Large Tropical River, India

Carbon studies in tropical rivers have gained significance since it was realized that a significant chunk of anthropogenic CO₂ emitted into the atmosphere returns to the biosphere, that is eventually transported by the river and locked up in coastal sediments for a few thousand years. Carbon studies are also significant because dissolved organic carbon (DOC) is known to complex the toxic trace metals in the river and carry them in the dissolved form. For the first time, this work has made an attempt to study the variations in DOC concentrations in space and time for a period of 19 months, and estimate their fluxes in the largest peninsular Indian river, the Godavari at Rajahmundry. Anthropogenic influence on DOC concentrations possibly from the number of bathing ghats along the banks and domestic sewage discharge into the river are evident during the pre-monsoon of 2004 and 2005. The rise in DOC concentrations at the onset of monsoon could be due to the contributions from flood plains and soils from the river catchment. Spatial variations highlighted that the DOC concentrations in the river are affected more by the anthropogenic discharges in the downstream than in the upstream. The discharge weighted DOC concentrations in the Godavari river is 3–12 times lower than Ganga-Brahmaputra, Indus and major Chinese rivers. The total carbon fluxes from the Godavari into the Bay of Bengal is insignificant (0.5%) compared to the total carbon discharges by major rivers of the world into oceans.     

Multidimensional fluorescence studies of the phenolic content of dissolved organic carbon in humic substances

Indicators suggest that the amount of dissolved organic carbon (DOC) in natural waters may be increasing. Climate change has been proposed as a potential contributor to the trend, and under such a mechanism, the phenolic content of DOC may also be increasing. This study explores the assessment of the phenolic character of DOC using multidimensional fluorescence spectroscopy as a more convenient alternative to traditional wet chemistry methods. Parallel factor analysis (PARAFAC) is applied to fluorescence excitation emission matrices (EEMs) of humic samples to analyze inherent phenolic content. The PARAFAC results are correlated with phenol concentrations derived from the Folin-Ciocalteau reagent-based method. The reagent-based method reveals that the phenolic content of five International Humic Substance Society (IHSS) samples varies from approximately 5.2 to 22 ppm Tannic Acid Equivalents (TAE). A four-component PARAFAC fit is applied to the EEMs of the IHSS sample dataset and it is determined by PARAFAC score correlations with phenol concentrations from the reagent-based method that components C2, C3, and C4 have the highest probability of containing phenolic groups. The results show the potential for PARAFAC analysis of multidimensional fluorescence data for monitoring the phenolic content of DOC.     

溶解性有机碳对微库仑法测定水中可吸附有机卤素的影响

微库仑法测水样中可吸附有机卤素(AOX)受多种因素影响,其中溶解性有机碳(DOC)的影响非常显著。DOC对微库仑法2种前处理方法(双柱法和振荡法)的影响差异很大。双柱法受DOC影响较小,当DOC浓度小于1 000 mg/L时,AOX加标回收率范围为94.0%~104%。振荡法受DOC影响较明显,随着DOC浓度的升高,AOX回收率持续下降,当DOC浓度达到1 000 mg/L时,AOX加标回收率下降至72.1%,但DOC浓度小于100 mg/L时,AOX加标回收满足方法要求。进一步研究发现,DOC对振荡法的影响主要由于竞争吸附降低了活性炭对AOX的吸附容量,而非吸附速率,虽然增大活性炭用量可在一定程度上减小DOC对AOX测定的影响,但对样品进行稀释是减少DOC影响的最简单高效的办法。同时,DOC对不同类型的有机卤代物影响不同,有机溴受DOC影响程度小于有机氯。     

Predicting Water Quality Impaired Stream Segments using Landscape-Scale Data and a Regional Geostatistical Model: A Case Study in Maryland

In the United States, probability-based water quality surveys are typically used to meet the requirements of Section 305(b) of the Clean Water Act. The survey design allows an inference to be generated concerning regional stream condition, but it cannot be used to identify water quality impaired stream segments. Therefore, a rapid and cost-efficient method is needed to locate potentially impaired stream segments throughout large areas. We fit a set of geostatistical models to 312 samples of dissolved organic carbon (DOC) collected in 1996 for the Maryland Biological Stream Survey using coarse-scale watershed characteristics. The models were developed using two distance measures, straight-line distance (SLD) and weighted asymmetric hydrologic distance (WAHD). We used the Corrected Spatial Akaike Information Criterion and the mean square prediction error to compare models. The SLD models predicted more variability in DOC than models based on WAHD for every autocovariance model except the spherical model. The SLD model based on the Mariah autocovariance model showed the best fit (r² = 0.72). DOC demonstrated a positive relationship with the watershed attributes percent water, percent wetlands, and mean minimum temperature, but was negatively correlated to percent felsic rock type. We used universal kriging to generate predictions and prediction variances for 3083 stream segments throughout Maryland. The model predicted that 90.2% of stream kilometers had DOC values less than 5 mg/l, 6.7% were between 5 and 8 mg/l, and 3.1% of streams produced values greater than 8 mg/l. The geostatistical model generated more accurate DOC predictions than previous models, but did not fit the data equally well throughout the state. Consequently, it may be necessary to develop more than one geostatistical model to predict stream DOC throughout Maryland. Our methodology is an improvement over previous methods because additional field sampling is not necessary, inferences about regional stream condition can be made, and it can be used to locate potentially impaired stream segments. Further, the model results can be displayed visually, which allows results to be presented to a wide variety of audiences easily.     

Modelling Dissolved Organic Carbon Turnover in Humic Lake Örträsket, Sweden

The organic carbon balance of a lake with high input of allochthonous organic carbon is modelled integrating physical, chemical and biological processes. The physical model captures the behaviour of real thermal stratification in the lake for different flow situations during the period 1993–1997. The dissolved organic carbon model is based on simulated trajectories of water parcels. By tracking parcels, account is kept of environmental factors such as temperature and radiation as well as DOC quality for each parcel. The DOC concentration shows seasonal variations primarily dependent on inflow. The organic matter degradation (bacterial- and photodegradation) in the lake amounts to 1.5–2.5 mg C l^–1 yr^–1, where photooxidation is responsible for approximately 10%. The estimated DIC production in the lake is large compared to sediment mineralisation and primary production. The main conclusion is that the model with the selected parameterisations of the degradation processes reasonably well describes the DOC dynamics in a forest lake.     

Impact of sampling strategy on stream load estimates in till landscape of the Midwest

Accurately estimating various solute loads in streams during storms is critical to accurately determine maximum daily loads for regulatory purposes. This study investigates the impact of sampling strategy on solute load estimates in streams in the US Midwest. Three different solute types (nitrate, magnesium, and dissolved organic carbon (DOC)) and three sampling strategies are assessed. Regardless of the method, the average error on nitrate loads is higher than for magnesium or DOC loads, and all three methods generally underestimate DOC loads and overestimate magnesium loads. Increasing sampling frequency only slightly improves the accuracy of solute load estimates but generally improves the precision of load calculations. This type of investigation is critical for water management and environmental assessment so error on solute load calculations can be taken into account by landscape managers, and sampling strategies optimized as a function of monitoring objectives.     

The role of forest type in the variability of DOC in atmospheric deposition at forest plots in Italy

Dissolved organic carbon (DOC) was studied in atmospheric deposition samples collected on a weekly basis in 2005-2009 at 10 forest plots in Italy. The plots covered a wide range of geographical attributes and were representative of the main forest types in Italy. Both spatial and temporal variations in DOC concentrations and fluxes are discussed, with the aim of identifying the main factors affecting DOC variability. DOC concentration increased from bulk to throughfall and stemflow water samples at all sites, as an effect of leaching from leaves and branches, going from 0.7-1.7 mg C L(-1) in bulk samples to 1.8-15.8 mg C L(-1) in throughfall and 4.2-10.7 mg C L(-1) in stemflow, with striking differences among the various plots. Low concentrations were found in runoff (0.5-2.0 mg C L(-1)), showing that the export of DOC via running waters was limited. The seasonality of DOC in throughfall samples was evident, with the highest concentration in summer when biological activity is at a maximum, and minima in winter due to limited DOC production and leaching. Statistical analysis revealed that DOC had a close relationship with organic and total nitrogen, and with nutrient ions, and a negative correlation with precipitation amount. Forest type proved to be a major factor affecting DOC variability: concentration and, to a lesser extent, fluxes were lower in stands dominated by deciduous species. The character of evergreens, and the size and shape of their leaves and needles, which regulate the interception mechanism of dry deposition, are mainly responsible for this.     

Fluorescence spectroscopic characterization of dissolved organic matter fractions in soils in soil aquifer treatment

This work investigated the effect of soil aquifer treatment (SAT) operation on the fluorescence characteristics of dissolved organic matter (DOM) fractions in soils through laboratory-scale soil columns with a 2-year operation. The resin adsorption technique (with XAD-8 and XAD-4 resins) was employed to characterize the dissolved organic matter in soils into five fractions, i.e., hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N), and hydrophilic fraction (HPI). The synchronous fluorescence spectra revealed the presence of soluble microbial byproduct- and humic acid-like components and polycyclic aromatic compounds in DOM in soils, and SAT operation resulted in the enrichment of these fluorescent materials in all DOM fractions in the surface soil (0–12.5 cm). More importantly, the quantitative method of fluorescence regional integration was used in the analysis of excitation–emission matrix (EEM) spectra of DOM fractions in soils. The cumulative EEM volume (Φ _{T, n} ) results showed that SAT operation led to the enrichment of more fluorescent components in HPO-A and TPI-A, as well as the dominance of less fluorescent components in HPO-N, TPI-N, and HPI in the bottom soil (75–150 cm). Total Φ _{T, n} values, which were calculated as $ {\Phi_{{T,n}}} \times {\mathrm{DOC}} $ , suggested an accumulation of fluorescent organic matter in the upper 75 cm of soil as a consequence of SAT operation. The distribution of volumetric fluorescence among five regions (i.e., P _{i, n} ) results revealed that SAT caused the increased content of humic-like fluorophores as well as the decreased content of protein-like fluorophores in both HPO-A and TPI-A in soils.     

Comparing removal of trace organic compounds and assimilable organic carbon (AOC) at advanced and traditional water treatment plants

Stability of drinking water can be indicated by the assimilable organic carbon (AOC). This AOC value represents the regrowth capacity of microorganisms and has large impacts on the quality of drinking water in a distribution system. With respect to the effectiveness of traditional and advanced processing methods in removing trace organic compounds (including TOC, DOC, UV₂₅₄, and AOC) from water, experimental results indicate that the removal rate of AOC at the Cheng Ching Lake water treatment plant (which utilizes advanced water treatment processes, and is hereinafter referred to as CCLWTP) is 54%, while the removal rate of AOC at the Gong Yuan water treatment plant (which uses traditional water treatment processes, and is hereinafter referred to as GYWTP) is 36%. In advanced water treatment units, new coagulation–sedimentation processes, rapid filters, and biological activated carbon filters can effectively remove AOC, total organic carbon (TOC), and dissolved organic carbon (DOC). In traditional water treatment units, coagulation–sedimentation processes are most effective in removing AOC. Simulation results and calculations made using the AutoNet method indicate that TOC, TDS, NH₃-N, and NO₃-N should be regularly monitored in the CCLWTP, and that TOC, temperature, and NH₃-N should be regularly monitored in the GYWTP.     

水质参数的遥感反演和遥感监测

遥感技术由于具有快速、宏观、低成本和周期性的优点,便于探测水质的时空变化,已成为水质参数监测的重要手段。目前能够直接进行遥感反演的水质参数主要是悬浮物浓度、叶绿素a浓度、可溶解性有机物等光学活性物质,并已经建立了许多反演模型。但是这些模型直接用于水质的遥感监测仍存在一些问题。今后,利用3S技术将地面观测和遥感观测结合起来,可望推动水色遥感的实际应用。