Treatment of an explosives plume in groundwater using an organic mulch biowall

A field demonstration of a mulch permeable reactive barrier (PRB), or “biowall,” as an in situ treatment technology for explosives in groundwater is summarized. Organic mulch consists of insoluble carbon biopolymers that are enzymatically hydrolyzed during decomposition to release aqueous total organic carbon (TOC). The released TOC is then available for microorganisms to use as an electron donor to transform electrophilic contaminants via reductive pathways. A 100‐foot‐long and 2‐foot‐thick mulch biowall was installed at the Pueblo Chemical Army Depot in Colorado to treat a shallow groundwater plume containing hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX). To discourage groundwater flow bypassing around and under the biowall in this highly permeable formation, a hydraulic control was installed and the PRB was keyed into the bedrock. Technology performance was monitored using a monitoring well network to establish the development and extent of the downgradient treatment zone. Performance objectives of the field demonstration were: (1) greater than 90 percent removal of RDX across the PRB and the treatment zone; (2) an RDX concentration of less than 0.55 μg/L in the treatment zone; and (3) cumulative toxic intermediate concentration (nitroso intermediates of RDX, MNX, DNX, and TNX) of less than 20 percent of the upgradient RDX concentration. All performance objectives were met within seven months after installation once the system reached a pseudo‐steady state. By this point, a sustained reducing/treatment zone had been created downgradient of the mulch PRB that showed greater than 93 percent RDX removal, RDX concentrations less than 0.55 μg/L, and no accumulation of toxic intermediates. The mulch biowall implemented during this demonstration was successful at meeting performance objectives while addressing the majority of potential concerns of the technology. © 2009 Wiley Periodicals, Inc.     

Modeling of water quality downgradient of a mulch biowall

Groundwater treatment biowalls may be located close to a surface water body to prevent contaminant discharge from a groundwater plume into the surface water. Groundwater contaminants passing through the biowall are treated within the biowall or immediately downgradient of the biowall. Biowalls designed and constructed for the treatment of chlorinated solvents typically contain either a solid and/or liquid source of organic carbon to promote contaminant degradation by enhanced anaerobic reductive dechlorination. Common solid organic materials in biowalls include wood mulch or similar waste plant material, and common liquid organic materials are vegetable oil (possibly emulsified) or other long‐chain fatty acids. Such biowalls then develop anaerobic conditions in the constructed biowall volume, and potentially downgradient, as dissolved oxygen originally present in the aquifer is consumed. This groundwater condition can lead to the appearance of sulfide if groundwater influent to the biowall contains moderate to high sulfate concentrations. Other researchers have presented evidence for groundwater conditions downgradient of a biowall or a permeable reactive barrier (PRB) that are altered in relation to groundwater quality, besides the desired effect of contaminant degradation or removal by precipitation. The objective of this work was to investigate with modeling the changes in downgradient groundwater species chemistry as a result of a constructed biowall. This was accomplished with a chemical species model to predict levels of sulfate and sulfide present in groundwater in close downgradient proximity to the biowall. The results indicate that downgradient chemical changes could impact a surface water body to which groundwater discharges. The model described could be enhanced by incorporating additional design variables that should be considered in biowall feasibility assessments.     

Applications of mulch biowalls—three case studies

Mulch biowalls are proving to be an effective means of generating reducing conditions for the in situ anaerobic reduction of contaminants in groundwater that are amenable to the reduction process. Mulch is an inexpensive and readily available substrate that provides a long‐lasting carbon and electron donor source for the stimulation of the anaerobic reduction process in groundwater. Examples of contaminants that are amenable to the biotic anaerobic reduction process include: chlorinated alkenes and alkanes, explosives, perchlorate, some metals, and petroleum hydrocarbons. The microbial degradation of cellulose fibers (mulch) is arguably the oldest reduction process known and is evident anywhere that plant material, soil, and water are present together. This article presents three case studies discussing three different uses of mulch biowalls to stimulate the anaerobic bioremediation of contaminants in shallow soils and groundwater. © 2009 Wiley Periodicals, Inc.     

Long‐term evaluation of an EHC injection permeable reactive barrier in a sulfate‐rich,high‐flow aquifer

Permeable reactive barriers (PRBs) have traditionally been constructed via trenching backfilled with granular, long‐lasting materials. Over the last decade, direct push injection PRBs with fine‐grained injectable reagents have gained popularity as a more cost‐efficient and less‐invasive approach compared to trenching. A direct push injection PRB was installed in 2005 to intercept a 2,500 feet (760 meter) long carbon tetrachloride (CT) groundwater plume at a site in Kansas. The PRB was constructed by injecting EHC^® in situ chemical reduction reagent slurry into a line of direct push injection points. EHC is composed of slow‐release plant‐derived organic carbon plus microscale zero‐valent iron (ZVI) particles, specifically formulated for injection applications. This project was the first full‐scale application of EHC into a flow‐through reactive zone and provided valuable information about substrate longevity and PRB performance over time. Groundwater velocity at the site is high (1.8 feet per day) and sulfate‐rich (~120 milligrams per liter), potentially affecting the rate of substrate consumption and the PRB reactive life. CT removal rates peaked 16 months after PRB installation with >99% removal observed. Two years post‐installation removal rates decreased to approximately 95% and have since stabilized at that level for the 12 years of monitoring data available after injection. Geochemical data indicate that the organic carbon component of EHC was mostly consumed after 2 years; however, reducing conditions and a high degree of chloromethane treatment were maintained for several years after total organic carbon concentrations returned to background. Redox conditions are slowly reverting and have returned close to background conditions after 12 years, indicating that the PRB may be nearing the end of its reactive life. Direct measurements of iron have not been performed, but stoichiometric demand calculations suggest that the ZVI component of EHC may, in theory, last for up to 33 years. However, the ZVI component by itself would not be expected to support the level of treatment observed after the organic carbon substrate had been depleted. A longevity of up to 5 years was originally estimated for the EHC PRB based on the maximum expected longevity of the organic carbon substrate. While the organic carbon was consumed faster than expected, the PRB has continued to support a high degree of chloromethane treatment for a significantly longer time period of over 12 years. Recycling of biomass and the contribution from a reduced iron sulfide mineral zone are discussed as possible explanations for the sustained reducing conditions and continued chloromethane treatment.     

Site characterization to support permeable reactive barrier design

Careful design studies and selection of an effective technique for the installation of permeable reactive barriers (PRBs) are important contributors to the overall success of zero‐valent iron PRBs. This article provides a case study summarizing the successful design and construction of a PRB installed at the former Carswell Air Force Base located in Fort Worth, Texas. Expedited site characterization using a cone penetrometer rig equipped with a mass spectrometer was employed to provide real‐time characterization and lithologic data. These data proved to be invaluable for the design of the PRB and allowed for the development of an accurate preconstruction cost estimate. Field data gained from the expedited water quality and geologic characterization along with aquifer testing and a bench‐scale treatability study provided a comprehensive basis for the design. The biopolymer slurry construction technique provided additional unanticipated benefits to the designed zero‐ valent iron treatment by promoting the development of anaerobic conditions favorable for microbial degradation of trichloroethene. Postconstruction monitoring data are discussed to illustrate the successful performance of the PRB. © 2005 Wiley Periodicals, Inc.     

Construction of a permeable reactive barrier in a residential neighborhood

In June 2001, the Massachusetts Department of Environmental Protection (DEP) installed a permeable reactive barrier (PRB) within a roadway in Needham, Massachusetts, to treat a plume of chlorinated solvents migrating toward two public water‐supply wells located in the adjacent town of Wellesley, Massachusetts. The solvents originated from an electronics manufacturer located approximately 2,300 feet upgradient of the roadway and 5,200 feet upgradient of the public supply wells. Chlorinated solvents, primarily trichloroethene (TCE), had migrated past the roadway to within 300 feet of the public supply wells. Two contaminant transport models prepared by the DEP's design contractor and the EPA indicated that the plume would reach the well field if no response actions were taken. To mitigate the future impact to the municipal well field, the DEP decided to install a PRB composed of zero‐valent granular iron across the path of the plume along Central Avenue in Needham. Though several dozen PRBs have been installed at sites worldwide and the technology is no longer considered innovative, the application of the technology in a roadway that receives 17,000 vehicles per day within a residential neighborhood is unique and presented difficulties not typically associated with PRB installations. The Needham PRB was also one of the first zero‐valent iron PRBs installed using the slurry trench method to treat chlorinated compounds. © 2002 Wiley Periodicals, Inc.     

Carbon speciation in ash, residual waste and contaminated soil by thermal and chemical analyses

Carbon in waste can occur as inorganic (IC), organic (OC) and elemental carbon (EC) each having distinct chemical properties and possible environmental effects. In this study, carbon speciation was performed using thermogravimetric analysis (TGA), chemical degradation tests and the standard total organic carbon (TOC) measurement procedures in three types of waste materials (bottom ash, residual waste and contaminated soil). Over 50% of the total carbon (TC) in all studied materials (72% in ash and residual waste, and 59% in soil) was biologically non-reactive or EC as determined by thermogravimetric analyses. The speciation of TOC by chemical degradation also showed a presence of a non-degradable C fraction in all materials (60% of TOC in ash, 30% in residual waste and 13% in soil), though in smaller amounts than those determined by TGA. In principle, chemical degradation method can give an indication of the presence of potentially inert C in various waste materials, while TGA is a more precise technique for C speciation, given that waste-specific method adjustments are made. The standard TOC measurement yields exaggerated estimates of organic carbon and may therefore overestimate the potential environmental impacts (e.g. landfill gas generation) of waste materials in a landfill environment.     

Ensuring the continued success of a mulch biowall at a trichloroethylene-contaminated superfund site: Lessons learned

Trichloroethylene (TCE) is a toxic organic compound, which can adversely affect human health. The chemical is one of the most frequently found contaminants in groundwater in the United States and around the world. A landfill in Maryland contaminated with high levels of TCE decades ago was added to the U.S. Environmental Protection Agency's National Priority List (NPL) in 1994. A biowall was installed on the site in 2013 to promote the bioremediation of TCE and subsequently of its degradation products. Six-year monitoring data indicated a steady removal of >99% groundwater TCE at the wall since installation. However, a concurrent buildup of intermediate byproducts was observed downgradient of the wall. An examination of the entire system was necessary to find the reason behind the inefficiency of the biowall. In this study, the background of the site, remediation plan, and installation were assessed. Monitoring data, including the concentration of TCE and its degradation byproducts, and geochemical and physical characteristics were evaluated to understand the conditions and challenges facing decision-makers of this project and possible options to improve biowall efficacy.     

Evaluation of soil solid amendments for TCE biodegradation in a biobarrier system

Permeable biobarrier systems (PBSs) are being recognized as low‐cost passive bioremediation technologies for chlorinated organic contamination. This innovative technology can play a crucial and effective role in site restorations. Laboratory‐scale experiments were conducted to investigate the biodegradation of trichloroethylene (TCE) to ethylene in shallow groundwater through the use of a PBS enhanced by bioaugmentation at the U.S. Department of Energy's Savannah River Site (SRS). Two composts and two plant amendments, eucalyptus mulch (EM) and corncobs (CC), were examined for their effectiveness at creating and maintaining conditions suitable for TCE anaerobic dechlorination. These materials were evaluated for their (1) nutrient and organic carbon content, (2) TCE sorption characteristics, and (3) longevity of release of nutrients and soluble carbon in groundwater to support TCE dechlorination. Native bacteria in the columns had the ability to convert TCE to dichloroethenes (DCEs); however, the inoculation with the TCE‐degrading culture greatly increased the rate of biodegradation. This caused a significant increase in by‐product concentration, mostly in the form of DCEs and vinyl chloride (VC) followed by a slow degradation to ethylene. Of the tested amendments, eucalyptus mulch was the most effective at supporting the reductive dechlorination of TCE. Corncobs created a very acidic condition in the column that inhibited dechlorination. © 2007 Wiley Periodicals, Inc.     

Evidence for biodegradation and volatilisation of dissolved petroleum hydrocarbons during in situ air sparging in large laboratory columns

Laboratory column experiments run for up to 13 days compared air sparging of groundwater contaminated by dissolved petroleum hydrocarbons in sterile and non-sterile aquifer sediments as well as uncontaminated sediments and groundwater. Loss of dissolved BTEX compounds in the contaminated columns was very rapid, occurring through volatilisation. The majority of the dissolved total organic carbon (TOC) persisted for much longer periods however. A direct comparison between losses from sterile and non-sterile columns suggested a negligible contribution of biodegradation to the removal of TOC. This was difficult to confirm through examination of O₂ utilisation because oxidation of a small amount of reduced sulphur in the aquifer materials was the dominant sink for O₂. Despite this, it was possible to conclude that less than 22% of the removal of TOC was through biodegradation during the first three days of air sparging.     

Remediation of chlorinated ethenes,ethanes, and methanes in groundwater using carbon‐ and iron‐based electron donor

Field‐scale pilot tests were performed to evaluate enhanced reductive dechlorination (ERD) of dissolved chlorinated solvents at a former manufacturing facility located in western North Carolina (the site). Results of the site assessment indicated the presence of two separate chlorinated solvent–contaminated groundwater plumes, located in the northern and southern portions of the site. The key chlorinated solvents found at the site include 1,1,2,2‐tetrachloroethane, trichloroethene, and chloroform. A special form of EHC^® manufactured by Adventus Americas was used as an electron donor at this site. In this case, EHC is a pH‐buffering electron donor containing controlled release carbon and ZV Iron MicroSphere 200, a micronscale zero‐valent iron (ZVI) manufactured by BASF. Approximately 3,000 pounds of EHC were injected in two Geoprobe^® boreholes in the saprolite zone (southern plume), and 3,500 pounds of EHC were injected at two locations in the partially weathered rock (PWR) zone (northern plume) using hydraulic fracturing techniques. Strong reducing conditions were established immediately after the EHC injection in nearby monitoring wells likely due to the reducing effects of ZV Microsphere 200. After approximately 26 months, the key chlorinated VOCs were reduced over 98 percent in one PWR well. Similarly, the key chlorinated solvent concentrations in the saprolite monitoring wells decreased 86 to 99 percent after initial increases in concentrations of the parent chlorinated solvents. The total organic carbon and metabolic acid concentrations indicated that the electron donor lasted over 26 months after injection in the saprolite aquifer. © 2009 Wiley Periodicals, Inc.     

Long-term Performance of a Permeable Reactive Barrier in Acid Sulphate Soil Terrain

Deep drainage technique utilised for flood mitigation in low-land coastal areas of Australia during the late 1960s has resulted in the generation of sulphuric acid in soil by the oxidation of pyritic materials. Further degradation of the subsurface environment with widespread contamination of the underlying soil and groundwater presents a major and challenging environmental issue in acid sulphate soil (ASS) terrains. Although several ASS remediation techniques recently implemented in the floodplain of Southeast Australia including operation of gates, tidal buffering and lime injections could significantly control the pyrite oxidation, they could not improve the long-term water quality. More recently, permeable reactive barriers (PRBs) filled with waste concrete aggregates have received considerable attention as an innovative, cost-effective technology for passive in situ clean up of groundwater contamination. However, long-term efficiency of these PRBs for treating acidic groundwater has not been established. This study analyses and evaluates the performance of a field PRB for treating the acidic water over 2.5 years. The pilot-scale alkaline PRB consisting of recycled concrete was installed in October 2006 at a farm of southeast New South Wales for treating ASS-impacted groundwater. Monitoring data of groundwater quality over a 30 month period were assessed to evaluate the long-term performance of the PRB. Higher pH value (~pH 7) of the groundwater immediately downstream of the PRB and higher rates of iron (Fe) and aluminium (Al) removal efficiency (>95%) over this study period indicates that recycled concrete could successfully treat acidic groundwater. However, the overall pH neutralising capacity of the materials within the barrier declined with time from an initial pH 10.2 to pH 7.3. The decline in the performance with time was possibly due to the armouring of the reactive material surface by the mineral precipitates in the form of iron and aluminium hydroxides and oxyhydroxides as indicated by geochemical modelling.     

Mobility of organic carbon from incineration residues

Dissolved organic carbon (DOC) may affect the transport of pollutants from incineration residues when landfilled or used in geotechnical construction. The leaching of dissolved organic carbon (DOC) from municipal solid waste incineration (MSWI) bottom ash and air pollution control residue (APC) from the incineration of waste wood was investigated. Factors affecting the mobility of DOC were studied in a reduced 2(6-1) experimental design. Controlled factors were treatment with ultrasonic radiation, full carbonation (addition of CO2 until the pH was stable for 2.5h), liquid-to-solid (L/S) ratio, pH, leaching temperature and time. Full carbonation, pH and the L/S ratio were the main factors controlling the mobility of DOC in the bottom ash. Approximately 60 weight-% of the total organic carbon (TOC) in the bottom ash was available for leaching in aqueous solutions. The L/S ratio and pH mainly controlled the mobilization of DOC from the APC residue. About 93 weight-% of TOC in the APC residue was, however, not mobilized at all, which might be due to a high content of elemental carbon. Using the European standard EN 13 137 for determination of total organic carbon (TOC) in MSWI residues is inappropriate. The results might be biased due to elemental carbon. It is recommended to develop a TOC method distinguishing between organic and elemental carbon.     

Chemical speciation of carbon in municipal solid waste incinerator residues

Incinerators do not achieve a complete mineralization of organic constituents of municipal solid waste. The solid residues (bottom ash, boiler ash and air pollution control residues) contain carbon which can be determined as total organic carbon (TOC). This work focuses on the TOC composition and its significance to the genesis and diagenesis of the solid residues. An analytical procedure is presented to characterize carbon species by different chemical and microscopic analytical methods. The procedure is based on two steps. In the first step a quantitative classification of TOC into four different carbon species (elemental carbon, water extractable organic carbon, dichloromethane extractable organic carbon and non extractable organic carbon) is performed to obtain a first survey of the TOC composition. Based on this survey a further characterization of individual carbon species is performed. The results of the qualitative and quantitative characterization of carbon species allow to postulate hypotheses on the influence of organic carbon on the long-term behavior of the solid residues.     

An evaluation of permeable reactive barrier projects in California

Permeable reactive barriers made of zero‐valent iron (ZVI PRBs) have become a prominent remediation technology in addressing groundwater contamination by chlorinated solvents. Many ZVI PRBs have been installed across the United States, some as research projects, some at the pilot scale, and many at full scale. As a passive and in situ remediation technology, ZVI PRBs have many attractive features and advantages over other approaches to groundwater remediation. Ten ZVI PRBs installed in California were evaluated for their performance. Of those ten, three are discussed in greater detail to illustrate the complexities that arise when quantifying the performance of ZVI PRBs, and to provide comment on the national debate concerning the downgradient effects of source‐zone removal or treatment on plumes of contaminated groundwater. © 2009 Wiley Periodicals, Inc.     

Seven‐year performance evaluation of a permeable reactive barrier

In June and July 2001, the Massachusetts Department of Environmental Protection (MassDEP) installed a permeable reactive barrier (PRB) to treat a groundwater plume of chlorinated solvents migrating from an electronics manufacturer in Needham, Massachusetts, toward the Town of Wellesley's Rosemary Valley wellfield. The primary contaminant of concern at the site is trichloroethene (TCE), which at the time had a maximum average concentration of approximately 300 micrograms per liter directly upgradient of the PRB. The PRB is composed of a mix of granular zero‐valent iron (ZVI) filings and sand with a pure‐iron thickness design along its length between 0.5 and 1.7 feet. The PRB was designed to intercept the entire overburden plume; a previous study had indicated that the contaminant flux in the bedrock was negligible. Groundwater samples have been collected from monitoring wells upgradient and downgradient of the PRB on a quarterly basis since installation of the PRB. Inorganic parameters, such as oxidation/reduction potential, dissolved oxygen, and pH, are also measured to determine stabilization during the sampling process. Review of the analytical data indicates that the PRB is significantly reducing TCE concentrations along its length. However, in two discrete locations, TCE concentrations show little decrease in the downgradient monitoring wells, particularly in the deep overburden. Data available for review include the organic and inorganic analytical data, slug test results from nearby bedrock and overburden wells, and upgradient and downgradient groundwater‐level information. These data aid in refining the conceptual site model for the PRB, evaluating its performance, and provide clues as to the reasons for the PRB's underperformance in certain locations. © 2008 Wiley Periodicals, Inc.     

Effect of liquid-to-solid ratio on semi-solid Fenton process in hazardous solid waste detoxication

The liquid-to-solid ratio (L/S) of semi-solid Fenton process (SSFP) designated for hazardous solid waste detoxication was investigated. The removal and minimization effects of o-nitroaniline (ONA) in simulate solid waste residue (SSWR) from organic arsenic industry was evaluated by total organic carbon (TOC) and ONA removal efficiency, respectively. Initially, Box-Behnken design (BBD) and response surface methodology (RSM) were used to optimize the key factors of SSFP. Results showed that the removal rates of TOC and ONA decreased as L/S increased. Subsequently, four target initial ONA concentrations including 100 mg kg⁻¹, 1 g kg⁻¹, 10 g kg⁻¹, and 100 g kg⁻¹ on a dry basis were evaluated for the effect of L/S. A significant cubic empirical model between the initial ONA concentration and L/S was successfully developed to predict the optimal L/S for given initial ONA concentration for SSFP. Moreover, an optimized operation strategy of multi-SSFP for different cases was determined based on the residual target pollutant concentration and the corresponding environmental conditions. It showed that the total L/S of multi-SSFP in all tested scenarios was no greater than 3.8, which is lower than the conventional slurry systems (L/S ? 5). The multi-SSFP is environment-friendly when it used for detoxication of hazardous solid waste contaminated by ONA and provides a potential method for the detoxication of hazardous solid waste contaminated by organics.     

高盐有机化工废水中COD与TOC的相关性

以COD为指标评价废水的有机物污染程度存在诸多不足，而TOC能更好地反映废水中有机物的含量。以高盐有机化工废水为研究对象，利用多级活性炭吸附工艺对其进行预处理，对原水、吸附出水、再生液中COD与TOC的相关性进行了分析。分析结果表明：在一定范围内，原水COD与TOC满足关系式COD = 56.537 7+ 0.967 04TOC；废水在吸附处理过程中，COD与TOC仍呈线性相关关系，但不同工段需各自建立独立的回归方程；TOC测定结果的精密度较好，且远优于COD直接测定的精密度，回收率范围98.59%~110.69%；利用线性回归方程根据TOC测定结果预测COD，预测结果准确、可靠、精密度好。     

Threshold amounts of organic carbon needed to initiate reductive dechlorination in groundwater systems

Aquifer sediment and groundwater chemistry data from 15 Department of Defense facilities located throughout the United States were collected and analyzed with the goal of estimating the amount of natural organic carbon needed to initiate reductive dechlorination in groundwater systems. Aquifer sediments were analyzed for hydroxylamine and NaOH‐extractable organic carbon, yielding a probable underestimate of potentially bioavailable organic carbon (PBOC). Aquifer sediments were also analyzed for total organic carbon (TOC) using an elemental combustion analyzer, yielding a probable overestimate of bioavailable carbon. Concentrations of PBOC correlated linearly with TOC with a slope near one. However, concentrations of PBOC were consistently five to ten times lower than TOC. When mean concentrations of dissolved oxygen observed at each site were plotted versus PBOC, it showed that anoxic conditions were initiated at approximately 200 mg/kg of PBOC. Similarly, the accumulation of reductive dechlorination daughter products relative to parent compounds increased at a PBOC concentration of approximately 200 mg/kg. Concentrations of total hydrolysable amino acids (THAA) in sediments also increased at approximately 200 mg/kg, and bioassays showed that sediment CO₂ production correlated positively with THAA. The results of this study provide an estimate for threshold amounts of bioavailable carbon present in aquifer sediments (approximately 200 mg/kg of PBOC; approximately 1,000 to 2,000 mg/kg of TOC) needed to support reductive dechlorination in groundwater systems. © 2012 Wiley Periodicals, Inc.     

Levels and Characteristics of TOC in Throughfall, Forest Floor Leachate and Soil Solution in Undisturbed Boreal Forest Ecosystems

Total organic carbon (TOC) concentrations and fluxes in throughfall, forest floor leachate, soil solution (15 and 35 cm depths), and groundwater for coniferous forest sites in the boreal zone throughout Finland are described. Eight upland forest stands and one peatland forest stand are included in the study and the samples were collected during 1991–1997. Carbon (C) pools in the living tree biomass and soil compartments are presented, and the hydrophobic/hydrophilic and acidic components of dissolved organic carbon (DOC) in samples collected in autumn 1999 and spring 2000 from two of the sites are compared. Biomass (aboveground and belowground) pools of C averaged 88 Mg ha^-1 and soil (humus layer + 20 cm soil layer) averaged 55 Mg ha^-1. Stand throughfall TOC monthly mean concentrations ranged from 4.0 to 18.6 mg L^-1 and annual fluxes averaged 4.0 g m^-2 yr^-1. TOC concentrations in the water passing through the forest floor and soil decreased with depth. Plot mean concentrations at 35 cm depth values ranged from 4.1 to 21.2 mg L^-1 and fluxes averaged 3.7 g m^-2 yr^-1. Throughfall TOC concentrations were lowest during the winter, snowfall period and highest during the growing season. No monotonic trends in throughfall TOC concentrations over the 1991–1997 period were found. Soil solution TOC concentrations varied considerably, both within and between years. DOC in throughfall, forest floor, and soil solutions and in both autumn and spring seasons was dominated by hydrophobic fractions, particularly acids. Spruce canopies and litter appear to be important sources of soluble organic carbon, particularly acidic and hydrophobic compounds. Further studies on the nature and dynamics of organic carbon fluxing through coniferous, boreal forest ecosystems are needed.