Kinetics of peat soil dissolved organic carbon release from bed sediment to water. Part 1. Laboratory simulation

Temporary water reservoirs built upon peat soil may exhibit water quality impairment from elevated dissolved organic carbon (DOC). Microbiological decay of the organic carbon in the bed with subsequent release produces "tea" colored water which may require treatment prior to use. This paper describes laboratory experiments designed to obtain data on the release process of DOC from soils containing 0.65%, 10% and 19% carbon. Parallel experiments with and without sodium azide treatment clearly distinguished the initial release of a porewater residual fraction and the microbial produced fraction. A one to two day quick-release DOC fraction, which ranges from 28% to 50%, first emerged from the bed, Step-1. This was followed by a constant rate of DOC production over four weeks, Step-2. The Step-2 average production rates were 3.4, 12, and 31 mg DOC/kg(dry)/day for the respective soils and increased as soil carbon content increased. The inorganic carbon (IC) behaved oppositely; its rate of production decreased with increasing soil carbon. A consistent and simple rate equation described the Step-2 DOC production process. This and other evidence obtained provided the basis for developing a mathematical model that couples both steps of the bed-to-water DOC release chemodynamics. The model is presented in a companion paper (Part-2).     

Size and XAD fractionations of trihalomethane precursors from soils

Soil organic matter is an important source of allochthonous dissolved organic matter inputs to the Sacramento-San Joaquin Delta waterways, which is a drinking water source for 22 million people in California, USA. Knowledge of trihalomethane (THM) formation potential of soil-derived organic carbon is important for developing effective strategies for organic carbon removal in drinking water treatment. In this study, soil organic carbon was extracted with electrolytes (deionized H2O and Na- or Ca-based electrolytes) of electrical conductivity bracketing those found in Delta leaching and runoff conditions. The extracts were physically and chemically separated into different fractions: colloidal organic carbon (0.45-0.1 microm), fine colloidal organic carbon (0.1-0.025 microm), and dissolved organic carbon (DOC) (<0.025 microm); hydrophobic acid (HPOA), transphilic acid, and hydrophilic acid. Two representative Delta soils, Rindge Muck (a peat soil) and Scribner Clay Loam (a mineral soil) were examined. Results showed that less than 2% of soil organic carbon was electrolyte-extractable and heterogeneous organic fractions with distinct THM reactivity existed. Regardless of soil and electrolytes, DOC and HPOA fractions were dominant in terms of total concentration and THMFP. The amounts of extractable organic carbon and THMFP were dependent on the cation and to a lesser extent on electrical conductivity of electrolytes. Along with our previous study on temperature and moisture effects on DOC production, we propose a conceptual model to describe the impacts of agricultural practices on DOC production in the Delta. DOC is mainly produced in the surface peat soils during the summer and is immobilized by accumulated salt in the soils. DOC is leached from soils to drainage ditches and finally to the Delta channels during winter salt leaching practices.     

Laboratory column studies for evaluating a barrier system for providing oxygen and substrate for TCE biodegradation

The industrial solvent trichloroethylene (TCE) is among the most ubiquitous chlorinated compounds found in groundwater contamination. The objective of this study was to develop a biobarrier system containing oxygen-organic releasing material to enhance the aerobic cometabolism of TCE in situ. The oxygen-organic material, which contains calcium peroxide and peat, is able to release oxygen and primary substrates continuously upon contact with water. Batch experiments were conducted to design and identify the components of the oxygen-organic releasing material, and evaluate the oxygen and organic substrate (presented as COD equivalent) release from the designed oxygen-organic material. The observed oxygen and chemical oxygen demand (COD) release rates were approximately 0.0246 and 0.052 mg/d/g of material, respectively. A laboratory-scale column experiment was then conducted to evaluate the feasibility of this proposed system for the bioremediation of TCE-contaminated groundwater. This system was performed using a series of continuous-flow glass columns including a soil column, an oxygen-organic material column, followed by two consecutive soil columns. Aerobic acclimated sludges were inoculated in all three soil columns to provide microbial consortia for TCE biodegradation. Simulated TCE-contaminated groundwater with a flow rate of 0.25 l/day was pumped into this system. Effluent samples from each column were analyzed for TCE and other indicating parameters (e.g., pH, dissolved oxygen). Results show that the decreases in TCE concentrations were observed over a 4-month operating period. Up to 99% of TCE removal efficiency was obtained in this passive system. Results indicate that the continuously released oxygen and organic substrates from the oxygen-organic materials enhanced TCE biotransformation. Thus, the biobarrier treatment scheme has the potential to be developed into an environmentally and economically acceptable remediation technology.     

Quantity and spectroscopic properties of soil dissolved organic matter (DOM) as a function of soil sample treatments: air-drying and pre-incubation

The dissolved organic matter (DOM) in soils is essentially defined by the way in which it is obtained. Therefore, we need to understand as to how pre-treatment of a soil will affect the characteristics of DOM, since this fraction may be strongly influenced by a soil's water content. The effect of two different pre-treatments on DOM from the A-horizons of a large variety of ecosystems and regions were compared. In both cases the soils were allowed to air-dry. In one case the air-dried soil was directly extracted (AD), while in the other case it was preincubated for 1 week at 50% of its water holding capacity (INCU). AD is simpler, but INCU brings the soil, and especially its microbial population, back to a standardised state, which is more representative of the usual state in the field. Both methods are used whenever an adjustment of the soil water content is essential to compare different regions or to eliminate short term weather effects. A significant regression indicated that the dissolved organic carbon (DOC) extracted from INCU samples was only 20% of AD DOC. Both the absorptivity (UV absorption divided by DOC) of 86% of the samples, and a fluorescence emission spectrum based Humification Index in all cases increased as a result of preincubation. This would indicate that labile compounds released during drying were metabolised during the incubation. However, the magnitude of this increase varied, and no correlation with soil organic and microbial carbon, pH, or texture could be detected. The results show that DOM extracted from AD and INCU soils is not comparable and that the differences are mainly due to the impact of air-drying on the microbial activity.     

土壤渗滤对有机微污染物去除性能研究

采用土壤柱试验研究了土壤渗滤对再生水中有机微污染物的去除性能。结果表明,土壤柱对再生水中的DOC、UV₂₅₄、总氮和总磷有较好的去除效果,并具有较高的抗冲击负荷的能力;土壤表层10 cm厚度对DOC的去除起主要作用;UV₂₅₄和AOX在土壤表层10 cm厚度降解效果不明显,随着深度增加去除率逐渐升高;液相色谱有机碳探测(LC-OCD)检测结果表明,土壤柱对溶解性有机物质的去除主要体现在对多糖物质的降解上,其次是有机酸类,对腐殖质也有一定的去除作用。     

Monitoring of effluent DOM biodegradation using fluorescence, UV and DOC measurements

The potential of effluent DOM to undergo microbial degradation was assessed in batch experiments. Effluent samples from Haifa wastewater treatment plant and Qishon reservoir (Greater Haifa wastewater reclamation complex, Israel) were incubated either with effluent or soil microorganisms for a period of 2-4 months and were characterized by dissolved organic carbon contents (DOC), UV(254) absorbance and by fluorescence excitation-emission matrices. Three main fluorescence peaks were identified that can be attributed to humic/fulvic components and "protein-like" structures. During biodegradation, specific fluorescences (F/DOC) of the three peaks were increased at various extents, suggesting selective degradation of non-fluorescing constituents. In some cases increase in the effluent fluorescence (F) was observed thus proposing (i) the formation of new fluorescing material associated with DOM biodegradation and/or (ii) degradation of certain organic components capable of quenching DOM fluorescence. Based on the ratio between fluorescence intensity and UV(254), different biodegradation dynamics for fluorescent DOM constituents as compared with other UV-absorbing molecules was delineated. Overall, about 50% of the total DOM was found to be readily degradable such that residual resistant DOC levels were between 8 and 10 mg l(-1). Enhanced levels of residual DOM in effluent-irrigated soils may contribute to the DOM pool capable of carrying pollutants to groundwater.     

Geochemical processes of mercury in Wujiangdu and Dongfeng reservoirs, Guizhou, China

The geochemical processes of mercury in Dongfeng (DF) and Wujiangdu (WJD) reservoirs, which were constructed in 1992 and 1979, respectively in Wujiang River, which is the upper branch of Yangtze River were investigated. One sampling site was chosen upriver of 1 km from the dam for each reservoir. Three sampling campaigns were conducted at these sampling sites in December 2003, April 2004 and July 2004, respectively. The distributions of different mercury species in the water column, sediment, and sediment pore water were studied. We found that the sediment is the net source of both inorganic and MeHg to the water column for both reservoirs. The MeHg diffusion fluxes in WJD reservoir at all sampling campaigns were significantly higher than those in DF reservoir. Our study demonstrated that the high primary productivity in the reservoir produced elevated organic matter content that would favor the methylmercury production in sediment.     

Influence of eutrophication on the coagulation efficiency in reservoir water

Water from the three reservoirs, Min-ter, Li-yu-ten and Yun-ho-shen, was examined for concentration of chlorophyll a, ultraviolet absorption (UV(254)), fluorescence intensity (FI), concentration of dissolved organic carbon (DOC), and fractionation of dissolved molecules by molecular weight. The water samples were collected over the change from spring to summer (May to July but before the typhoon season) when the water temperature and extent of eutrophication increase. Analytical results indicate that the concentration of DOC is proportional to the concentration of chlorophyll a, but not to the values of UV(254) and FI. Therefore, eutrophication, extraneous contaminants of small molecules, and the extracellular products of algae cause an increase in DOC, but a decrease in the proportion of large organic molecules such as of humic substances. The fraction of DOC with a molecular weight of less than 5000 Da increases with the concentration of chlorophyll a. All these data suggest that changes in the quality of water after eutrophication make the treatment of drinking water more difficult. The method of enhanced coagulation was recently developed for removing DOC. However, the results of this paper demonstrate that the efficiency of DOC removal falls as the degree of eutrophication increases. When the percentage of DOC with small molecules excreted by algae increased by 1%, the efficiency of DOC removal decreased by approximately 1%, implying that enhanced coagulation are not able to remove the DOC excreted by the algae during eutrophication, and resulting an increased concentration of trihalomethanes formation in water disinfections process.     

Intrinsic degradation of volatile fatty acids in laboratory-compacted clayey soil

Volatile fatty acids (VFAs) represent the major organic constituent of landfill leachate and provide the greatest potential for leachate induced organic contamination of groundwater (e.g. as represented by an increase in the concentration of dissolved organic carbon and chemical oxygen demand). Long-term diffusion tests were performed for laboratory-compacted clayey soil plugs exposed to continuous supply of synthetic leachate containing VFAs. Significant microbial activity developed upon exposure of the soil's indigenous microorganisms to these degradable contaminants. The growth of heterotrophic aerobic bacteria (HAB, which include facultative anaerobes), sulfate reducing bacteria (SRB) and methanogenic bacteria carrying out fermentation and mineralization of the VFAs became evident after 30-50 days of testing. The maximum microbial counts of (2-8) x 10(8) and (0.1-1) x 10(8) cfu/g for HAB and SRB were localized in the soil layer at the interface with the source of organic and inorganic nutrients. Regardless of this rapid growth in microbial population, the VFA consumption was small and measurable only after a lag of 140-180 days. It is considered that this lag of otherwise readily degradable organic compounds (such as VFAs) persisted due to a combination of the effects of a high initial concentration of these acids (2.4 g/l as dissolved organic carbon, DOC) applied to carbon starved soil microorganisms and the small pore size of the compacted clay. Once the significant amounts of gas were generated from fermentation, conditions developed for improved mass transport and exchange of the nutrients and bacteria and the outcome of the intrinsic degradation was more apparent. The breakdown of VFAs that followed after the lag was localized near the top of the soil and was characterized by a short half-life of 0.75-5 days for DOC (total VFAs as dissolved organic carbon).     

Dioxins, PCBs, and HCB in soil and peat profiles from a pristine boreal catchment

The aim of this study was to explore how atmospherically derived soil pollution is affected by environmental processes at two typical boreal catchment landscape type settings: wetlands and forested areas. Measurements of hydrophobic organic compounds (HOCs) in forest soil and peat from an oligotrophic mire at various depths were performed at a remote boreal catchment in northern Sweden. HOCs in peat were evenly distributed throughout the body of the mire while levels of HOCs in the forest soil increased with increased amount of organic matter. Evaluation of HOC composition by principal component analysis (PCA) showed distinct differences between surface soils and deeper soil and peat samples. This was attributed to vertical transport, degradation and/or shifting sources over time. The calculated net vertical transport differed between surface layers (0.3%) and deeper soils (8.0%), suggesting that vertical transport conditions and processes differ in the deeper layers compared to the surface layers.     

Improvement of DOC removal by multi-stage AOP-biological treatment

The single and multi-stages advanced oxidation process (AOP)-biological treatments were evaluated to apply for drinking water treatment, especially for the water containing less susceptible dissolved organic carbon (DOC) to ozone, comparing with the ozonation-biological treatment. Minaga reservoir water and the secondary effluent from a Municipal wastewater treatment plant were used as dissolved organic matter (DOM) solutions. DOC removals after 60 min AOP-biological treatment were 62% and 41% in the Minaga reservoir water and the secondary effluent, respectively, whereas those in the ozonation-biological treatment only 40% and 15% of DOC were removed, respectively. The result indicated that the single-stage AOP-biological treatment could improve DOC removal in comparison with the single-stage ozonation-biological treatment. This is because the AOP mineralized both biodegradable dissolved organic carbon (BDOC) produced in the early stage of oxidation and non-biodegradable dissolved organic carbon (NBDOC), whereas only BDOC was mineralized by further ozonation and NBDOC was not oxidized in the ozonation-biological treatment. The multi-stage treatment could not improve DOC removal in comparison with the single-stage treatment in the ozonation-biological treatment for the secondary effluent containing less susceptible DOC to ozone. However, the multi-stage AOP-biological treatment significantly reduced DOC and achieved 71% of DOC removal by 4 times repetition of 15 min oxidation, whereas DOC removal was 41% in the single-stage AOP-biological treatment for the same oxidation time. The improvement of DOC removal by the multi-stage AOP-biological treatment was due to BDOC removal as a radical scavenger by subsequent biological treatment in the early stage of oxidation and direct mineralization in the latter stage of oxidation.     

Leaching kinetics of water soluble organic carbon (WSOC) from upland soil.

The kinetics of the leaching process of Water Soluble Organic Carbon (WSOC) from an upland soil were studied in a column leaching experiment. The pattern of the leaching curve indicated multiphasic release kinetics. A conceptual model was proposed to divide capillary and gravitational pores. The translocation of organic carbon in soil during leaching occurs in four sequential steps. 1) degradation of insoluble organic carbon to form WSOC; 2) desorption into capillary pore water; 3) diffusion towards gravitation pore water; and 4) leaching by convection flow. The overall kinetics of the leaching process can be depicted using an equation with three additive terms for degradation, desorption/diffusion, and convection, respectively.     

Development of a combined isotopic and mass-balance approach to determine dissolved organic carbon sources in eutrophic reservoirs

A combined mass-balance and stable isotope approach was set up to identify and quantify dissolved organic carbon (DOC) sources in a DOC-rich (9 mg L⁻¹) eutrophic reservoir located in Western France and used for drinking water supply (so-called Rophemel reservoir). The mass-balance approach consisted in measuring the flux of allochthonous DOC on a daily basis, and in comparing it with the effective (measured) DOC concentration of the reservoir. The isotopic approach consisted, for its part, in measuring the carbon isotope ratios (δ¹³C values) of both allochthonous and autochthonous DOC sources, and comparing these values with the δ¹³C values of the reservoir DOC. Results from both approaches were consistent pointing out for a DOC of 100% allochthonous origin. In particular, the δ¹³C values of the DOC recovered in the reservoir (−28.5 ± 0.2‰; n = 22) during the algal bloom season (May-September) showed no trace of an autochthonous contribution (δ¹³C in algae = −30.1 ± 0.3‰; n = 2) being indistinguishable from the δ¹³C values of allochthonous DOC from inflowing rivers (−28.6 ± 0.1‰; n = 8). These results demonstrate that eutrophication is not responsible for the high DOC concentrations observed in the Rophemel reservoir and that limiting eutrophication of this reservoir will not reduce the potential formation of disinfection by-products during water treatment. The methodology developed in this study based on a complementary isotopic and mass-balance approach provides a powerful tool, suitable to identify and quantify DOC sources in eutrophic, DOC-contaminated reservoirs.     

Statistical modelling of water colour in the uplands: The Upper Midd catchment 1979-1987

The increasing colour of raw water from the uplands is a matter of concern to water managers. The colour record for the period 1979-1987 is examined for the catchment of Upper Nidderdale, North Yorkshire. The variation in colour shows a marked seasonality with peaks occurring during the autumn months. No long-term sustained increase in colour is found, although colour levels were high in 1980, 1985 and 1987. Colour is found to be highly correlated with iron and, more particularly, aluminium. There is no relationship between colour and turbidity which suggests that there is no direct link between colour levels and erosion on the catchments. Colour increases appear to relate to large soil moisture deficits in months immediately prior to the colour flush and to high soil moisture deficits in the previous year. Complementary relationships are found between monthly rainfall totals and colour. In the light of these findings, it is suggested that high colour is associated with water table lowering and aerobic decomposition of the upper organic peat layers.     

Impact of sewage sludge spreading on nickel mobility in a calcareous soil: adsorption–desorption through column experiments

A soil column adsorption–desorption study was performed on an agricultural calcareous soil to determine the impact of sewage sludge spreading on nickel mobility. Ni adsorption experiments were followed by desorption tests involving the following liquid extractants: water, calcium (100 mg/L), oxalic acid (525 mg/L equivalent to 100 mg carbon/L), and sludge extracts (0.5 and 2.5 g/L). Desorption tests were also conducted after sewage sludge spreading at three application rates (30, 75, and 150 t/ha). According to the breakthrough curve, Ni adsorption was irreversible and occurred mainly through interactions with calcite surface sites. Nickel desorption from the soil column was promoted in presence of significant dissolved organic carbon (DOC) concentration as observed with oxalic acid elution and sludge extract at 2.5 g/L. In sludge-amended soil columns, the maximum Ni levels occurred in first pore volumes, and they were positively correlated to the sludge application rate. The presence of DOC in leaching waters was the main factor controlling Ni desorption from the sludge-amended soil columns. This finding implies that DOC generated by sludge applied on calcareous soils might facilitate the leaching of Ni due to the formation of soluble Ni–organic complexes. Thus, sludge application can have potential environmental impacts in calcareous soils, since it promotes nickel transport by decreasing Ni retention by soil components.     

Mobility of isoproturon from an alginate-bentonite controlled release formulation in layered soil

The mobility of isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea] from an alginate-based controlled release (CR) formulation was investigated by using soil columns. A layered bed system simulating the typical arrangement under a plastic greenhouse, which is composed of sand, peat, amended soil and native soil was used. The CR formulation was based on sodium alginate (1.87%), isoproturon (1.19%), natural bentonite (3.28%), and water (93.66%), and was compared to technical grade isoproturon. The use of the alginate-bentonite CR formulation produced less vertical mobility of the active ingredient as compared to the technical product. There was no presence of herbicide in the leachate when the alginate-bentonite CR formulation was used. However, 0.90% of isoproturon appeared when the treatment was carried out with technical grade material. Isoproturon mobility was modelled using the programme CMLS, which showed the peat layer to retard pesticide leaching. Analysis of the soil columns showed the highest isoproturon concentration in the peat layer.     

不同人工湿地基质对污水总有机碳去除能力初探

选择4种常见基质及基质配比,研究其碳含量和组分对污水中总有机碳(TOC)的去除影响。结果显示当污水的TOC浓度为27 mg/L时,4种基质都向水体中释放碳,且释放碳的大小顺序为:砂子-土壤-泥炭混合基质土壤砂子-土壤混合基质砂子,基质的碳含量越高,释放到水体中碳越多。3种基质对水体中TOC的去除率大小顺序为:土壤砂子-土壤混合物基质砂子,基质碳含量越高,微生物活性越强,对TOC的去除率越高。在第12天,砂子-土壤-泥炭混合基质处理中TOC浓度的增加,与其稳结合态有机碳含量较高有关。有机碳含量和组分影响了人工湿地基质对TOC的去除。     

Characteristics of biotic and abiotic removals of dissolved organic carbon in wastewater effluents using soil batch reactors.

Biodegradable dissolved organic carbon (BDOC) analyses and abiotic adsorption of dissolved organic carbon (DOC) from different wastewater effluent were conducted to evaluate biotic and abiotic removal mechanisms as a function of the initial DOC concentration and source of DOC using soil batch reactors. To obtain high DOC concentrations, a laboratory-scale reverse osmosis unit was used. It was found that BDOC fraction was independent of the initial DOC concentration and was dependent on the source of wastewater and/or the types of wastewater treatment. The BDOC fractions varied from 9 to 73%. Trickling filter effluent (Tucson, Arizona) showed the highest BDOC, ranging from 65 to 73% biodegradable, while wastewater treated by the soil aquifer treatment (SAT) (NW-4) was found to be most refractory, with DOC removals of 9 to 14%. For nitrified/denitrified tertiary effluent (Mesa, Arizona) and secondary effluent (Scottsdale, Arizona), 36 to 42% removal of DOC was observed during the BDOC test. The amount of BDOC in the wastewater depended not on the concentration of DOC, but on the effectiveness of pretreatment. Abiotic adsorption capacity of wastewater effluent varied from 6 to 18%. Molecular weight distribution analyses showed that more than 50% of DOC in the Scottsdale concentrate had a molecular weight of less than 1000 Da, and no significant change in distribution profiles occurred after approximately 12% abiotic adsorption with both soils with acclimated microorganisms (SAT soil) and soils without acclimated microorganisms (non-SAT soils). Hence, preferential adsorption was not observed and the presence of acclimated microbes did not influence adsorption.     

Distribution and fractionation of phosphorus, cadmium, nickel, and lead in calcareous soils amended with composts

Composts improve organic carbon content and nutrients of calcareous soils but the accumulation and distribution of phosphorus and heavy metals among various fractions in soil may vary under the south Florida conditions. The accumulation of P, Cd, Ni, and Pb with depth and the distribution of water soluble, exchangeable, carbonate, Fe-Mn oxides, organic and residual forms of each element were investigated in soils amended with municipal solid waste (MSW) compost, co-compost and biosolids compost and inorganic fertilizer (as control). Total concentrations of P, Cd, Ni, and Pb were higher in the 0-22 cm soil layers and decreased considerably in the rock layers. These elements were in the decreasing order of P > Pb > Ni > Cd. Amounts of water soluble and exchangeable forms of P, Cd, Ni and Pb were negligible at 0-22 cm soil depths except for Cd in the 10-22 cm depth. Amending calcareous soil with either organic or inorganic amendments rendered phosphorus, nickle and lead in the residual form followed by Fe-Mn oxides form in the 0-10 and 10-22 cm soil layers. Cadmium was predominantly in the Fe-Mn oxides fraction followed by the residual and carbonate forms in both soil layers. A significant positive correlation was found between various organic carbon fractions and organic forms of P, Cd and Pb in the surface soil layer. Soil amended with MSW compost had higher concentration of Cd in the organic fraction whereas, co-compost and MSW compost amended soil had higher concentrations of organic Ni fraction in the 0-10 cm soil layer.