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.     

A brief overview of modern directions in marine DOC studies part II--recent progress in marine DOC studies

Progress made in analytical techniques allows the formulation of new concepts in the biogeochemistry of organic carbon. The second part of our review summarizes the latest evolution and introduces new ideas in the biogeochemistry of marine dissolved organic carbon (DOC). Via classification of different fractions and sources of DOC, characterization of its composition, age and availability for bacterial utilization, and fate of DOC, we show the role of DOC in the global carbon cycle and the significance of bulk DOC in the oceans. Special emphasis is placed on the microbial loop in the cycling of DOC and its relation with higher trophic levels (phytoplankton and zooplankton). Significant progress has also been made in the study of the roles of colloidal organic material in metal complexation, ultraviolet radiation in dissolved organic matter photochemical oxidation, and chromophore-containing constituents of DOC as the signature of DOC for satellite observations. The importance of bulk DOC in the global carbon cycle requires the inclusion of this fraction in the regional and global carbon models. We predict that future DOC study in the ocean will focus on the development of sophisticated, almost continuously recording, moored DOC instrument arrays for the monitoring of small-scale DOC horizontal and vertical patchiness; widespread time series stations including estuarine, coastal and open environments; more detailed chemical characterization of different fractions of organic carbon from diverse marine habitats; parameterization of predictive models of DOC cycling on regional and global scales, incorporating the microbial loop; and finally, monitoring of DOC dynamics from satellites on regional and global scales.     

Estimation of chlorophyll a content in inland turbidity waters using WorldView-2 imagery: a case study of the Guanting Reservoir,Beijing, China

Complex optical properties, such as non-pigment suspension and colored dissolved organic matter (CDOM), make it difficult to achieve accurate estimations of remotely sensed chlorophyll a (Chla) content of inland turbidity. Recent attempts have been made to estimate Chla based on red and near-infrared regions where non-pigment suspension and CDOM have little effect on water reflectance. The objective of this study is to validate the applicability of WV-2 imagery with existing effective estimation methods from MERIS when estimating Chla content in inland turbidity waters. The correlation analysis of measured Chla content and WV-2 imagery bands shows that the Chla sensitive bands of WV-2 are red edge, NIR 1, and NIR 2. The coastal band is designed for seawater Chla detection. However, the high correlation with turbidity data and low correlation with Chla made coastal band unsuitable for estimating Chla in inland waters. The high-resolution water body images were extracted by combining the spectral products (NDWI) with the spatial morphological products (sobel edge detection). The estimation results show that the accuracy of the single band and NDCI is not as good as the two-band method, three-band method, stepwise regression algorithm (SRA) and support vector machines (SVM). The SVM estimation accuracy was the highest with an R², RMSE, and URMSE of 0.8387, 0.4714, and 19.11%, respectively. This study demonstrates that the two-band and three-band methods are effective for estimating Chla in inland water for WV-2 imagery. As a high-precision estimation method, SVM has great potential for inland turbidity water Chla estimation.     

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.     

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.     

Mercury proxies and mercury dynamics in a forested watershed of the US Northeast

Although many studies focus on mercury (Hg) and methylmercury (MeHg) dynamics in streams, challenges remain in identifying the relative importance of land cover and seasonality at regulating Hg and MeHg dynamics at the watershed scale. Developing robust proxies for Hg and/or MeHg determination also remains a challenge. Our study used Hg, MeHg, and dissolved organic carbon (DOC) concentration measurements and various DOC fluorescence indices to characterize Hg and DOC dynamics in a forested watershed of the US Northeast. Principal component analysis indicated that land cover/landscape position (i.e., headwater vs. wetland-influenced area vs. lake-influenced area) explained 44 % of the variance in Hg, MeHg, DOC concentrations, and DOC quality during the snow-free season, while seasonality (i.e., air temperature and discharge) explained only 21 % of the variance in the results. Furthermore, finding a good proxy for Hg that is valid across a range of landscape positions remains a challenge; however, regression analysis indicated that the fluorescence peak Humic C (excitation?=?350 nm; emission?=?max (420–480)), which corresponds to the presence of melanoidins in water, explained 21 % of the variability in MeHg concentrations across both space and time (p?=?0.001), and thus appears to be a possible proxy for MeHg determination in our study watershed. From a management perspective, land cover modifications (lake, reservoir, and wetland) are likely to play more important roles at regulating Hg, MeHg, and DOC exports at the watershed scale than long-term changes in the climate of this region.     

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.     

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.     

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。     

Generalized regression neural network (GRNN)-based approach for colored dissolved organic matter (CDOM) retrieval: case study of Connecticut River at Middle Haddam Station,USA

The prediction of colored dissolved organic matter (CDOM) using artificial neural network approaches has received little attention in the past few decades. In this study, colored dissolved organic matter (CDOM) was modeled using generalized regression neural network (GRNN) and multiple linear regression (MLR) models as a function of Water temperature (TE), pH, specific conductance (SC), and turbidity (TU). Evaluation of the prediction accuracy of the models is based on the root mean square error (RMSE), mean absolute error (MAE), coefficient of correlation (CC), and Willmott’s index of agreement (d). The results indicated that GRNN can be applied successfully for prediction of colored dissolved organic matter (CDOM).     

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.     

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.     

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.     

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.     

Simplifying and improving the extraction of nitrate from freshwater for stable isotope analyses

Determining the isotopic composition of nitrate (NO(3)(-)) in water can prove useful to identify NO(3)(-) sources and to understand its dynamics in aquatic systems. Among the procedures available, the 'ion-exchange resin method' involves extracting NO(3)(-) from freshwater and converting it into solid silver nitrate (AgNO(3)), which is then analysed for (15)N/(14)N and (18)O/(16)O ratios. This study describes a simplified methodology where water was not pre-treated to remove dissolved organic carbon (DOC) or barium cations (added to precipitate O-bearing contaminants), which suited samples with high NO(3)(-) (≥ 00 μM or 25 mg L(-1) NO(3)(-)) and low DOC (typically < 17 μM of C or 5 mg L(-1) C) levels. % N analysis revealed that a few AgNO(3) samples were of low purity (compared with expected % N of 8.2), highlighting the necessity to introduce quality control/quality assurance procedures for silver nitrate prepared from field water samples. Recommendations are then made to monitor % N together with % O (expected at 28.6, i.e. 3.5 fold % N) in AgNO(3) in order to better assess the type and gravity of the contamination as well as to identify potentially unreliable data.     

Biogeochemical patterns in a river network along a land use gradient

The Bode catchment (Germany) shows strong land use gradients from forested parts of the National Park (23 % of total land cover) to agricultural (70 %) and urbanised areas (7 %). It is part of the Terrestrial Environmental Observatories of the German Helmholtz association. We performed a biogeochemical analysis of the entire river network. Surface water was sampled at 21 headwaters and at ten downstream sites, before (in early spring) and during the growing season (in late summer). Many parameters showed lower concentrations in headwaters than in downstream reaches, among them nutrients (ammonium, nitrate and phosphorus), dissolved copper and seston dry mass. Nitrate and phosphorus concentrations were positively related to the proportion of agricultural area within the catchment. Punctual anthropogenic loads affected some parameters such as chloride and arsenic. Chlorophyll a concentration and total phosphorus in surface waters were positively related. The concentration of dissolved organic carbon (DOC) was higher in summer than in spring, whereas the molecular size of DOC was lower in summer. The specific UV absorption at 254 nm, indicating the content of humic substances, was higher in headwaters than in downstream reaches and was positively related to the proportion of forest within the catchment. CO₂ oversaturation of the water was higher downstream compared with headwaters and was higher in summer than in spring. It was correlated negatively with oxygen saturation and positively with DOC concentration but negatively with DOC quality (molecular size and humic content). A principle component analysis clearly separated the effects of site (44 %) and season (15 %), demonstrating the strong effect of land use on biogeochemical parameters.     

Establishment of a sampling strategy for the use of blue mussels as an indicator of organotin contamination in the coastal environment

The application of the Mussel Watch concept to the assessment of chemical contamination in the coastal environment is still premature, since the relationship between the physiological and ecological aspects of blue mussels and the accumulation of contaminants in their soft tissues remains unclear. We cannot yet directly estimate with known confidence the degree of chemical contamination from the levels of contaminants in the soft tissues of mussels. An understanding of the source and range of variability in the tissue concentrations of contaminants is essential, and the establishment of a biomonitoring sampling strategy to minimize the effect of identified sources of variability is required. The present study was conducted to clarify the characteristics of organotin accumulation in blue mussels under various conditions in Tokyo Bay, and to establish an optimized sampling strategy of mussels as exposure indicators of organotin contamination in Japan. It was clear that the sample number, individual size, spawning activity and vertical habitat were factors causing a variation of tissue concentration. Based on a quantitative estimation of the variability of organotin concentration in mussel tissues under various physiological and natural conditions, we suggest that a composite sample of 30 mussels (3-5 cm in shell length), collected from the infralittoral zone prior to their spawning season, is essential to reduce the variability between individuals and to obtain reproducible analytical values at a sampling site. For monitoring sites where natural blue mussels cannot be collected, an alternative method of transplanting blue mussels from a relatively clean area would be required.     

Changes in the sorption and rate of 17β-estradiol biodegradation by dissolved organic matter collected from different water sources

The potential biodegradation and subsequent transformation of 17β-estradiol (E2) to estrone (E1) were examined in the presence of various dissolved organic matter (DOM) isolated from effluent, river and lake waters. In addition, estrogenicity was estimated in association with the removal of E2 via its sorption onto DOM and biodegradation. The more biodegradable lake-derived DOM promoted more extensive transformation of E2 into E1 than the effluent organic matter through a biodegradation process. Overall, under all conditions, biodegradation dominated the removal of E2 in water. The increased dissolved organic carbon (DOC) concentrations in river and lake-derived DOM (e.g. 6.5 mg C L(-1)) reduced the removal of E2 by decreasing its biodegradation due to the moderate sorption of E2 onto DOM. The effluent organic matter showed greater removal of E2 via biodegradation, as well as significantly high sorption. This was associated with a large amount of hydrophobic fulvic acid (FA)- and humic acid (HA)-like organic components, as shown by the small increase in the specific UV absorbance at 254 nm (SUVA(254)). An increase in the DOC concentration reduced the removal of E2, resulting in high estrogenicity. The present study suggests that both organic composition and DOC concentration influenced the removal of E2 and, therefore, should be fully considered when assessing estrogenicity and its impacts on the aquatic environment.     

The development of a chemical 'fingerprint' to characterise dissolved organic matter in natural waters

A suite of twelve assays has been used to 'fingerprint' dissolved organic matter (DOM). The assays were applied directly to filtered natural water samples. Temperature, pH and conductivity accounted for the environmental conditions on-site. Bulk carbon characteristics were assayed by measuring UV absorbance at 200 and 240 nm, colour in grade Hazen, DOC (dissolved organic carbon), fluorescence (excitation 370 nm, emission 450 nm) and the complexation of phenol itself. Measuring hydroxybenzenes ('monophenolics'), polyhydroxybenzenes ('polyphenolics') and total phenolics with the Gibbs, Prussian Blue and Folin-Ciocalteau assays, respectively, determined the phenolics pool. The methodology was tested on six freshwater sites in North Wales chosen to provide differences in vegetation, land-use and water chemistry and sampled once during each season. A novel approach for the presentation of the data has been developed that combines all range normalised assay results for each site and each season within one polar plot, hence the term 'fingerprint'. The data was also analysed using principal component factor analysis. Assays characterised as determining the chemical properties of DOM contributed to Factor 1 and explained 59% of the variation in the data. Assays apparently determined by the water matrix, contributed to Factor 2 and explained 20% of the variation within the data. The factor scores obtained for each site showed more variation for assays relating to the chemical properties of DOM than to the surrounding water matrix. The methodology was found to detect chemical changes within DOM for each site throughout the year and different responses for different sites.     

Landscape Controls on Mercury in Streamwater at Acadia National Park, USA

Fall and spring streamwater samples were analyzed for total mercury (Hg) and major ions from 47 locations on Mount Desert Island in Maine. Samples were collected in zones that were burned in a major wildfire in 1947 and in zones that were not burned. We hypothesized that Hg concentrations in streamwater would be higher from unburned sites than burned watersheds, because fire would volatilize stored Hg. The Hg concentrations, based on burn history, were not statistically distinct. However, significant statistical associations were noted between Hg and the amount of wetlands in the drainage systems and with streamwater dissolved organic carbon (DOC). An unexpected result was that wetlands mobilized more Hg by generating more DOC in total, but upland DOC was more efficient at transporting Hg because it transports more Hg per unit DOC. Mercury concentrations were higher in samples collected at lower elevations. Mercury was positively correlated with relative discharge, although this effect was not distinguished from the DOC association. In this research, sample site elevation and the presence of upstream wetlands and their associated DOC affected Hg concentrations more strongly than burn history.