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

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

Concentrations and fluxes of dissolved organic carbon in UK topsoils

Dissolved organic carbon (DOC) concentrations in soil water samples collected from depths of 5 to 20 cm at 10 moorland and 11 forest sites during the period 2000-2006 were obtained from new measurements and from the monitoring programmes of the UK Environmental Change Network and the International Cooperative Programme (ICP) on Forests. Data on soil properties and vegetation type were also assembled. Considering data from Prenart tension collectors, which were used at nearly all the sites, mean annual concentrations ranged from 1.3 to 97.5 g m(-3) with means of 19.5 (standard deviation 15.2) and 27.6 (SD 23.3) g m(-3) for moorland and forest sites respectively. Interannual mean DOC concentration at an individual site varied by only 1.5-fold, averaged over all sites with at least three years' data. Concentrations during summer months (April to September) were on average 17% greater than those in winter (October to March). If data from two sites (the single peatland and an unusual forest site) were ignored, DOC concentrations were strongly inversely related to water flux, estimated from rainfall and evaporation data. Fluxes of DOC, calculated by combining concentration with water flux, ranged from 2.2 to 71.9 gC m(-2) yr(-1) over all sites and years, with overall means of 19.2 (SD 13.6) and 12.2 (SD 13.9) gC m(-2) yr(-1) for the moorland and forest sites respectively. However, if the two exceptional sites were omitted, the overall mean was 9.1 gC m(-)(2) yr(-1) with a standard deviation of only 4.9 gC m(-2) yr(-1). Annual DOC flux was strongly dependent upon annual water flux, varying by 3.5-fold between years when averaged over all sites. On average, 75.5% of the DOC was exported during the winter period (October to March).     

Changes in dissolved organic carbon during artificial recharge of groundwater in a forested esker in Southern Finland

Sprinkling infiltration in a forested esker leading to artificial recharge of groundwater was studied in Southern Finland. Changes in dissolved organic carbon (DOC) and the molecular size distribution and chemical properties of the organic carbon were investigated during the infiltration process. Artificial groundwater was produced using sprinkling infiltration directly onto the forest floor. One result of lake water infiltration through the organic horizon and 1 m thick mineral soil layer was a slight net increase in the DOC concentrations from 9.4 mg/L in the infiltration water to 13.2 mg/L in percolation water. This indicates that the forest soil represents a potential input of organic matter into infiltration water. However, the DOC concentrations decreased by 27–38% as the infiltration water percolated down through the unsaturated soil layer into the groundwater zone. At a distance of 1450 m from the infiltration area, the mean DOC concentration in the groundwater was below the recommended value for drinking water in Finland of 2.0 mg/L. There was a strong reduction in the concentrations of hydrophilic and hydrophobic acids, but only a slight decrease in hydrophilic neutral organic compounds during the infiltration process. The DOC in the production well consisted of low molecular size fractions. Larger molecular size fractions were removed effectively from the water during the infiltration process.     

Timing of organic carbon release from mountain pine beetle impacted ponderosa pine forests in South Dakota

The decay of mountain pine beetle (MPB) (Dendroctonus ponderosae) affected ponderosa pine (Pinus ponderosa) forests has increased organic carbon (OC) loading within the Rapid Creek watershed in the Black Hills of South Dakota, with total OC (TOC) concentrations up to 6.2 mg L^?1 observed in 2015. The impacts of large‐scale tree mortality on water quality were delayed. OC concentrations in the watershed correlated with recent MPB impact stage progression. Regional ponderosa pine forests that were 3 and 6 years after MPB infection (grey and snagfall phases) exhibited increased OC loading within the Rapid Creek watershed. A better understanding of regional watershed response patterns for MPB tree mortality may assist with mitigating ancillary water quality impacts.     

Atmospheric deposition of persistent organic pollutants to the East Rongbuk Glacier in the Himalayas

To assess levels and seasonal trends of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in a high-altitude mountain region, a 2.1 m snowpack sample was collected from the East Rongbuk Glacier at 6572 ma.s.l. on Mt. Everest in September 2005. This snowpack covered a full year period from the fall of 2004 to the summer of 2005 and reflected the major meteorology of the monsoon and non-monsoon seasons. The most abundant compounds detected in the snow samples were γ-hexachlorocyclohexane (γ-HCH) and α-HCH with mean concentrations of 123 pg L^− 1 and 92 pg L^− 1, respectively. This is the first detection of these compounds in recent snow samples from the Himalayas. Backward air trajectory analysis indicated that the Himalayas could be influenced by the major HCH source regions in both India and China. Among the seven marker PCB congeners (PCB 28, 52, 101, 118, 138, 153, and 180) quantified, PCB 28 and PCB 52 were the only dominant PCB congeners detected, with mean concentrations of 17 pg L^− 1 and 6 pg L^− 1, respectively. In addition, DDT metabolites, p,p′-DDE and p,p′-DDD were detected in some snow samples and mean concentrations of DDTs were 24 pg L^− 1. Seasonal differences were observed for α- and γ-HCH concentrations increasing from the non-monsoon season to the monsoon season. Meanwhile, PCB 28 and HCB showed uniform variations with peak concentrations resulting from an effective scavenging by snowfalls between the monsoon and non-monsoon interval. Compared to other high mountain areas, the levels of POPs deposited into the East Rongbuk Glacier were relatively low, resulting from the highest altitude and remoteness from source regions.     

Reconsidering the quantitative analysis of organic carbon concentrations in size exclusion chromatography

The evaluation of the molecular size distribution of natural organic matter (NOM) in aquatic environments via size exclusion chromatography (SEC) is important for the understanding of environmental processes such as nutrient cycling and pollutant transport as well as of technical water treatment processes. The use of organic carbon (OC) detectors has become popular in recent studies due to improved availability and quantification possibilities, which supposedly are superior to those of ultraviolet (UV) detectors. A set of 12 NOM samples was used to demonstrate the limitations of online OC detection (OCD) when analyzing complex aquatic organic matter. A novel evaluation approach for SEC data is introduced by combining the information from UV absorbance (UVA) and OCD chromatograms as well as offline total OC (t-OC) and dissolved OC-specific UVA (SUVA) measurements. It could be shown that about 70% of certain OC components were not detected with the OCD system used in this study. For the investigated samples, these types of carbon accounted for up to 72% of the t-OC, i.e. for such NOM samples quantification by OCD is not possible or at least highly questionable. The addition of an oxidant improved the overall oxidation efficiency only slightly. Most likely NOM that predominantly consists of polysaccharides and features a nominal molecular weight of 150 kg/mol or more was responsible for low OCD yields. For future applications, a further improvement of the OCD system would be worthwhile so that quantitative analytical data on the molecular size distribution of NOM and its structural characteristics such as the SUVA distribution can be obtained.     

Ultrafiltration of natural organic matter and black carbon: Factors influencing aggregation and membrane fouling

There are concerns about black carbon (BC), due to its potential for sorption of toxic pollutants and inevitably entering drinking water sources. This study aimed to evaluate factors affecting BC aggregation and membrane fouling in the ultrafiltration of river water. Hydrophilic carbon black (CB) was selected as a surrogate of submicron BC in natural waters. Calcium, pH, and natural organic matter (NOM) were found to influence CB aggregation. Calcium induced interparticle interactions in a pH range of 4.3-7.7. In river water at 0.3 mM Ca²⁺, CB remained as fine aggregates (<300 nm) that caused substantial filtration resistance. At 1.3 mM Ca²⁺, CB size increased to 2.2-3.3 μm and membrane fouling was reduced. Interactions between particles and NOM enhanced organic rejection and eliminated irreversible membrane fouling. BC in water resources is a noxious substance, but it was easily aggregated in hard waters and could enhance NOM removal in the ultrafiltration process.     

Relating freshwater organic matter fluorescence to organic carbon removal efficiency in drinking water treatment

Monthly raw and clarified water samples were obtained for 16 UK surface water treatment works. The fluorescence excitation-emission matrix (EEM) technique was used for the assessment of total organic carbon (TOC) removal and organic matter (OM) characterisation. The impact of algae presence in water on TOC removal, and its relationship with fluorescence, was analysed. Fluorescence peak C intensity was found to be a sensitive and reliable measure of OM content. Fluorescence peak C emission wavelength and peak T intensity (reflecting the degree of hydrophobicity and the microbial fraction, respectively) were found to characterize the OM; the impact of both on TOC removal efficiency was apparent. OM fluorescence properties were shown to predict TOC removal, and identify spatial and temporal variations. Previous work indicates that the trihalomethane (THM) concentration of treated water can be predicted from the raw water TOC concentration. The simplicity, sensitivity, speed of analysis and low cost, combined with potential for incorporation into on-line monitoring systems, mean that fluorescence spectroscopy offers a robust analytical technique to be used in conjunction with, or in place of, other approaches to OM characterisation and THM formation prediction.     

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

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

Variation in iron,aluminum and dissolved organic carbon mass transfer coefficients in lakes

Steady-state mass balance models have been successfully used to predict annual loads and concentrations of numerous substances in lakes. A major limitation of the model is that the value of the mass transfer coefficient, nu(X), for some substance, X, is assumed constant and is taken as a mean value of a set of calibration lakes. The range in mean values between lakes for nu(X) is typically two- to three-fold. Thus, there is some potential for error in model predictions if the true but unknown value for a given lake differs from the mean, calibration value. Moreover, the use of a region-specific value for nu(X) for all lakes in a region means that when environmental conditions change, the model will have to be re-calibrated requiring many more years of monitoring. In this study, mass balances for two substances, total iron and aluminum, are presented along with simple empirical relationships that predict mass transfer coefficients for iron as a function of dissolved organic carbon (DOC) concentration and aluminum as a function of DOC and pH. The relationships, which are consistent with current understanding of iron and aluminum behavior, account for >90% of the variation in nu(X). Improvements in mass balance model predictions are expected when these coefficients are used in place of constant values.     

河南商丘地区土壤有机碳密度及其空间分布特征

利用多目标地球化学调查数据,对商丘地区表层(0~20 cm)、中上层(0~100 cm)和全层(0~200 cm)土壤有机碳密度及其储量进行了估算,并分析不同土壤类型、地貌类型及土地利用类型下土壤有机碳密度的空间分布特征及影响因素。结果表明:研究区土壤碳库以无机碳为主,表层、中上层、全层有机碳密度分别为2.34 kg/m~2、2.82 kg/m~2、7.89 kg/m~2,均低于全国平均水平。在不同土壤类型、地貌类型及土地利用类型间有机碳密度存在显著差异,土壤有机碳含量及分布受气候及土壤理化性质影响不明显,温度是主要影响因子。     

An overall isotherm for activated carbon adsorption of dissolved natural organic matter in water

Design and analysis of activated carbon processes in water treatment often requires the adsorption isotherm for dissolved natural organic matter (NOM). Of the isotherm models available, the Summers and Roberts (SR) equation, capable of describing the adsorbent dose effect with the fewest parameters, has been successfully used to normalize NOM isotherm data. In this study, we show that the adsorbent dose in the SR equation can be eliminated as an intermediate variable and the initial concentration effect on NOM adsorption is then described explicitly. Comparing with the original SR equation, the derived isotherm equation is in a form more amenable to analysis. To ensure that the prediction is physically attainable, we introduced the limiting adsorption capacity by taking the adsorbent pore volume and size exclusion into consideration. Subsequently, we develop a simple relationship that can be used to determine the minimum adsorbent usage required for any desirable level of treatment. By comparing with extensive isotherm data previously published by Li et al. [2003a. Polydisperse adsorbability composition of several natural and synthetic organic matrices. J. Colloid Interface Sci. 265(2), 265-275], we demonstrated that the isotherm equation derived herein yields predictions that agree with the much more complicated fictive component-ideal adsorbed solution theory (IAST)-based model for NOM from different sources and over a range of initial concentrations.     

Trends in hydrometeorological conditions and stream water organic carbon in boreal forested catchments

Temporal trends in stream water total organic carbon (TOC) concentration and export were studied in 8 forested headwater catchments situated in eastern Finland. The Seasonal Kendall test was conducted to identify the trends and a mixed model regression analysis was used to describe how catchment characteristics and hydrometeorological variables (e.g. precipitation, air and stream water temperatures, and atmospheric deposition) related to the variation in the concentration and export of stream water TOC. The 8 catchments varied in size from 29 to 494 ha and in the proportion of peatland they contained, from 8 to 70%. Runoff and TOC concentration were monitored for 15-29 years (1979-2006). Trends and variation in TOC levels were analysed from annual and seasonal time series. Mean annual TOC concentration increased significantly in seven of the eight catchments. The trends were the strongest in spring and most apparent during the last decade of the study period. The slopes of the trends were generally smaller than the variation in TOC concentration between years and seasons and between catchments. The annual TOC export showed no clear trends and values were largely determined by the temporal variability in runoff. Annual runoff showed a decreasing trend in two of the eight catchments. Mean annual air and stream water temperatures showed increasing trends, most clearly seen in the summer and autumn series. According to our modeling results, stream water temperature, precipitation and peatland percentage were the most important variables explaining annual and most seasonal TOC concentrations. The atmospheric deposition of SO₄, NH₄, and NO₃ decreased significantly over the study period, but no significant link with TOC concentration was found. Precipitation was the main hydrometeorological driver of the TOC export. We concluded that stream water TOC concentrations and exports are mainly driven by catchment characteristics and hydrometeorological factors rather than trends in atmospheric acid deposition.     

Characterization of natural organic matter adsorption in granular activated carbon adsorbers

The removal of natural organic matter (NOM) from lake water was studied in two pilot-scale adsorbers containing granular activated carbon (GAC) with different physical properties. To study the adsorption behavior of individual NOM fractions as a function of time and adsorber depth, NOM was fractionated by size exclusion chromatography (SEC) into biopolymers, humics, building blocks, and low molecular weight (LMW) organics, and NOM fractions were quantified by both ultraviolet and organic carbon detectors. High molecular weight biopolymers were not retained in the two adsorbers. In contrast, humic substances, building blocks and LMW organics were initially well and irreversibly removed, and their effluent concentrations increased gradually in the outlet of the adsorbers until a pseudo-steady state concentration was reached. Poor removal of biopolymers was likely a result of their comparatively large size that prevented access to the internal pore structure of the GACs. In both GAC adsorbers, adsorbability of the remaining NOM fractions, compared on the basis of partition coefficients, increased with decreasing molecular size, suggesting that increasingly larger portions of the internal GAC surface area could be accessed as the size of NOM decreased. Overall DOC uptake at pseudo-steady state differed between the two tested GACs (18.9 and 28.6 g-C/kg GAC), and the percent difference in DOC uptake closely matched the percent difference in the volume of pores with widths in the 1-50 nm range that was measured for the two fresh GACs. Despite the differences in NOM uptake capacity, individual NOM fractions were removed in similar proportions by the two GACs.     

Reducing the concentration of assimilable organic carbon (AOC) in treated drinking water

This study focuses on reducing the concentration of assimilable organic carbon (AOC) in treated drinking water. Experiments were conducted to evaluate the efficiency of AOC removal by biological activated carbon filters (BACF) in a pilot-scale system. The measured values of AOC in treated drinking water were approximately 59.0 ± 8.6 μg acetate-C/L. The results show that BACFs reduce the total concentration of AOC. The concentration of AOC primarily indicates microbial growth in a water supply network, and the amount of AOC in the water is significantly reduced after BACF treatment. After BACF treatment, the removal of AOC was approximately 58% after 40 min of empty-bed contact time. An AOC empirical equation was established by determining the relationship between water quality parameters, such as total organic carbon, dissolved organic carbon, UV₂₅₄, ammonia nitrogen, and total phosphorous.     

Mechanistic and kinetic evaluation of organic disinfection by-product and assimilable organic carbon (AOC) formation during the ozonation of drinking water

Ozonation of drinking water results in the formation of low molecular weight (LMW) organic by-products. These compounds are easily utilisable by microorganisms and can result in biological instability of the water. In this study, we have combined a novel bioassay for assessment of assimilable organic carbon (AOC) with the detection of selected organic acids, aldehydes and ketones to study organic by-product formation during ozonation. We have investigated the kinetic evolution of LMW compounds as a function of ozone exposure. A substantial fraction of the organic compounds formed immediately upon exposure to ozone and organic acids comprised 60-80% of the newly formed AOC. Based on experiments performed with and without hydroxyl radical scavengers, we concluded that direct ozone reactions were mainly responsible for the formation of small organic compounds. It was also demonstrated that the laboratory-scale experiments are adequate models to describe the formation of LMW organic compounds during ozonation in full-scale treatment of surface water. Thus, the kinetic and mechanistic information gained during the laboratory-scale experiments can be utilised for upscaling to full-scale water treatment plants.     

Heterogeneity of natural organic matter from the Chena River,Alaska

Water samples were collected in July 2001 from the Chena River in central Alaska. The natural organic matter (NOM) was size fractionated into particulate (POM,>0.45 microm), colloidal (COM,1kDa-0.45 microm) and dissolved (DOM,<1k Da) organic matter fractions, using filtration and ultrafiltration. The size-fractionated organic matter was then analyzed for organic carbon (OC) and nitrogen (N), isotopic (delta13C and delta15N) and molecular composition, using continuous flow isotope ratio mass spectrometry and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Results of phase partitioning showed that, on average, about 6% of OC and 16% of N occurred in the form of POM while 66% of OC and 57% of N occurred in the form of COM, and 28% of the OC and 27% of the N were in the DOM form. Organic matter in the river water was found to be highly heterogeneous in terms of chemical composition and isotopic signatures. The C/N ratio was as low as 16+/-1 in the POM (n=2) to as high as 48+/-1 in the COM (n=3) and 38+/-4 in the DOM (n=3), suggesting a diagenetically younger POM. Values of delta13C increased with decreasing size, varying from -29.59+/-0.45% in the POM to -27.47+/-0.06% in the COM to -16.93+/-0.08% in the DOM. In contrast, values of delta15N decreased with decreasing size, from 2.64% in POM to 1.64% in COM to 1.33% in DOM. These results, together with radiocarbon measurements, suggest a preferential decomposition of lighter C isotope (12C) and heavier N isotopic (15N) from POM to COM to DOM. Results of py-GC/MS showed that the percentage of polysaccharides decreased with decreasing size, further supporting a degradation pathway of NOM from POM to COM and DOM in Chena River waters. More studies are needed to examine the seasonal and spatial variations of size-fractionated organic matter.     

Spatial and temporal variability in the relationship between water colour and dissolved organic carbon in blanket peat pore waters

The transfer of carbon from terrestrial peat to the fluvial environment forms an important component of the peatland carbon cycle, and has major implications for water quality. Dissolved organic carbon (DOC) is generally considered the largest constituent of aquatic carbon and tends to be the most intensively monitored, particularly in peatland catchments. However, many long-term records for DOC are based on proxy studies that use water colour as a surrogate. This paper tests the robustness of using spectrophotometric techniques to monitor water colour, based on absorbance from a single wavelength at 400 nm, as a surrogate for true DOC determination. The general ability of spectrophotometric analysis to measure low DOC concentrations depends on the calibration used; thus, the minimum mass of DOC detectable varies considerably and in this study was found to be as high as 10.32 mg C L^− 1. While there is often a significant correlation between water colour and DOC, it was found that the use of single or even “pooled” regressions to predict DOC concentrations could result in miscalculations of more than 50%. Further, the water colour-DOC relationship in blanket peat pore waters was found to vary significantly between peat layers, land management treatments and through time. Thus, studies using long-term water colour records as a proxy for long-term DOC concentrations in peatlands must be treated with a certain degree of caution, especially in cases where changes may have taken place to DOC production, such as those caused by land management change, during the course of investigation.     

Using soil biomass as an indicator for the biological removal of effluent-derived organic carbon during soil infiltration

This study investigates the relationship between soil biomass and organic carbon removal during the infiltration of conventionally treated effluents used for groundwater recharge during soil-aquifer treatment (SAT). Investigations were conducted on samples collected from full-scale SAT sites, revealing a positive correlation between biodegradable organic carbon (BOC) concentrations in the recharged effluents and total viable soil biomass concentrations in the infiltration zone of soil samples collected from respective recharge basins. Findings of this study suggest that BOC limits soil biomass growth and was able to support a steady-state concentration of viable soil biomass that is characteristic to BOC concentrations introduced with the recharged effluents. All investigated sites indicate that BOC is primarily removed within 30 cm soil depth leading to a significant increase in soil biomass levels (measured as substrate induced respiration (SIR), total viable biomass, and dehydrogenase activity (DHA)). Controlled biological column studies revealed that the primary components of BOC in domestic effluents are organic colloids. Findings of this study support that hydrophobic acids, commonly believed to be recalcitrant, may also be attenuated by biological processes during soil infiltration.     

Distribution of organic carbon in tropical mangrove sediments (Cochin,India)

Surficial sediments were sampled every month from three mangrove regions around the metropolis of Cochin (India). Sedimentary organic carbon content exhibited wide seasonal fluctuations. The hydrology of the mangrove system is regulated mainly by high rainfall during the monsoon and by tidal inundation. The results indicated the role of tidal activity and sediment texture in the preservation and retention of organic matter.