Contaminant Mass Balance Research Articles

Natural attenuation of dissolved petroleum fuel constituents in a fractured Chalk aquifer: contaminant mass balance with probabilistic analysis

A plume-scale mass balance is developed to assess the natural attenuation (NA) of dissolved organic contaminants in fractured, dual-porosity aquifers. This methodology can be used to evaluate contaminant distribution within the aquifer, plume source term, contaminant biodegradation and plume status. The approach is illustrated for a site on the UK Upper Chalk aquifer impacted by petroleum fuel containing methyl tert -butyl ether (MTBE) and tert -amyl methyl ether (TAME). Variability in site investigation data and uncertainty in the mass balance were assessed using probabilistic analysis. The analysis shows that benzene, toluene, m/p-xylene and o-xylene (BTEX) compounds are biodegraded primarily by denitrification and sulfate reduction in the aquifer, with an equivalent plume-scale first-order biodegradation rate of 0.49 a −1 . Other biodegradation processes are less important. Sorption contributes to hydrocarbon attenuation in the aquifer but is less important for MTBE and TAME. Uncertainty in the plume source term and site hydrogeological parameters had the greatest effect on the mass balance. The probabilistic analysis enabled the most likely long-term composition of the plume source term to be deduced and provided a site-specific estimate of contaminant mass flux for the prediction of plume development. The mass balance methodology provides a novel approach to improve NA assessments for petroleum hydrocarbons and other organic contaminants in these aquifer settings. Supplementary material: Plume organic chemistry, aquifer hydraulic conductivity and probability distribution functions used for mass balance inputs are available at https://doi.org/10.6084/m9.figshare.c.7016429 Thematic collection: This article is part of the Monitoring the aquifers collection available at: https://www.lyellcollection.org/topic/collections/monitoring-the-aquifers

An agenda for the future of Arctic snow research: the view from Svalbard

The Arctic region is warming at over twice the mean rate of the Northern Hemisphere and nearly four times faster than the globe since 1979. The local rate of warming is even higher in the European archipelago of Svalbard. This warming is transforming the terrestrial snow cover, which modulates surface energy exchanges with the atmosphere, accounts for most of the runoff in Arctic catchments and is also a transient reservoir of atmospherically deposited compounds, including pollutants. Improved observations, understanding and modelling of changes in Arctic snow cover are needed to anticipate the effects these changes will have on the Arctic climate, atmosphere, terrestrial ecosystems and socioeconomic factors. Svalbard has been an international hub of polar research for many decades and benefits from a well-developed science infrastructure. Here, we present an agenda for the future of snow research in Svalbard, jointly developed by a multidisciplinary community of experts. We review recent trends in snow research, identify key knowledge gaps, prioritize future research efforts and recommend supportive actions to advance our knowledge of present and future snow conditions pertaining to glacier mass balance, permafrost, surface hydrology, terrestrial ecology, the cycling and fate of atmospheric contaminants, and remote sensing of snow cover. This perspective piece addresses issues relevant to the circumpolar North and could be used as a template for other national or international Arctic research plans.

Effectiveness of hyperbaric chamber ventilation.

Hyperbaric chamber ventilation (HCV) refers to the intentional introduction of fresh gas, whether air, oxygen, or heliox, into a pressurised hyperbaric chamber in order to remove stale or otherwise compromised gas. The minimum required continuous HCV rate is usually determined by mathematical models derived from the contaminant mass balance within a well-stirred compartment. Non-uniform contaminant distribution patterns inside a hyperbaric chamber could emerge and invalidate the predictions of well-stirred models. Contaminant distribution was investigated inside a clinical hyperbaric chamber with the aim of comparing well-stirred model predictions with the actual contaminant concentration measurements. Local ventilation effectiveness inside a clinical hyperbaric chamber may be compromised, leading to higher contaminant concentration values compared to the predictions of a mathematical model with a well-stirred assumption. A well-stirred assumption in mathematical models is a useful simplification that allows reasonably accurate estimates of HCV requirements. However, local ventilation effectiveness values in a particular hyperbaric chamber might vary, with the potential for hazardous contaminant accumulation in under-ventilated zones.

Occurrence, removal, and mass balance of contaminants of emerging concern in biological nutrient removal-based sewage treatment plants: Role of redox conditions in biotransformation and sorption

The study investigates the fate of 20 contaminants of emerging concern (CECs) in two full-scale wastewater treatment plants (WWTPs) based on the Biodenipho™ (WWTP 1) and anaerobic-anoxic-oxic (WWTP 2) processes. Samples of both the dissolved and solid phases (particulate and sludge) from all the wastewater and sludge processing-related units were studied using the mass balance approach to understand the distribution of CECs. The total mass load removal efficiency for anti-inflammatory (4), antibiotics (4), and hormones (5) was 76, 46, 93%, and 72, 38, 90% from WWTP 1 and 2, respectively. The mass load analysis showed that 8.3 kg and 6.5 kg of targeted contaminants enter the treatment plants per day while 0.35 kg and 0.32 kg are discharged along with effluent, and 1.5 g and 7.7 g (dry weight) are released through sludge in WWTP 1 and 2, respectively. Both biodegradation and sorption mechanisms depended on the redox conditions. Ammonia oxidizing conditions favoured the most for the biotransformation, followed by anaerobic and nitrate-reducing conditions. The study stresses the need for separate redox conditions for optimum removal of CECs and advanced tertiary treatment to remove recalcitrant compounds. The results help better understand the removal mechanisms of the CECs in BNR treatment.

Removal and formation of perfluoroalkyl substances in Canadian sludge treatment systems – A mass balance approach

Poly- and per-fluoroalkyl substances (PFAS) are an emerging class of anthropogenic contaminants whose occurrence has raised concerns with the beneficial reuse of biosolids from wastewater treatment. This study evaluated the behavior of thirteen PFAS in nine Canadian sludge treatment systems including pelletization, alkaline stabilization, aerobic and anaerobic digestion processes. The composition of the overall PFAS-fluorine (ΣPFAS-F) loading in a system fed with only primary sludge was dominated by perfluorodecanoate (PFDA), whereas systems with blended primary and waste activated sludge feeds had a mix of short and long chain PFAS in raw sludges and treated biosolids. An increase in average ΣPFAS-F mass flow was observed through pelletization (19% formation) and alkaline stabilization (99% formation) processes indicating negative removal or contaminant formation. One of the two aerobic digestion systems and three of the five anaerobic digestion systems showed modest reductions (< 40% removal) in ΣPFAS-F loading. Long chain PFAS such as perfluorodecanoate (PFDA) and perfluorooctane sulfonate (PFOS) exhibited a wide variation in behavior ranging from substantial formation (> 75% formation) to modest removal (42% removal) in the surveyed systems while short chain perfluoropentanoate (PFPeA) mass flows increased through the three systems where they occurred. Overall, the contaminant mass balances revealed that there were significant changes in mass flows of the target PFAS through all kinds of sludge treatment systems. The results of this study on PFAS fate through sludge processing can inform future global PFAS risk management activities as well as sludge treatment considerations.

Natural attenuation of a chlorinated ethene plume discharging to a stream: Integrated assessment of hydrogeological, chemical and microbial interactions

Attenuation processes of chlorinated ethenes in complex near-stream systems result in site-specific outcomes of great importance for risk assessment of contaminated sites. Additional interdisciplinary and comprehensive field research is required to enhance process understanding in these systems. In this study, several methods were combined in a multi-scale interdisciplinary in-situ approach to assess and quantify the near-stream attenuation of a chlorinated ethene plume, mainly consisting of cis-dichloroethene (cis-DCE) and vinyl chloride (VC), discharging to a lowland stream (Grindsted stream, Denmark) over a monitoring period of seven years. The approach included: hydrogeological characterisation, reach scale contaminant mass balance analysis, quantification of contaminant mass discharge, streambed fluxes of chlorinated ethenes quantified using Sediment Bed Passive Flux Meters (SBPFMs), assessment of redox conditions, temporal assessment of contaminant concentrations, microbial analysis, and compound-specific isotope analysis (CSIA). This study site exhibits a special attenuation behaviour not commonly encountered in field studies: the conversion from an initially limited degradation case (2012-16), despite seemingly optimal conditions, to one presenting notable levels of degradation (2019). Hence, this study site provides a new piece to the puzzle, as sites with different attenuation behaviours are required in order to acquire the full picture of the role groundwater‐surface water interfaces have in risk mitigation. In spite of the increased degradation in the near-stream plume core, the contaminant attenuation was still incomplete in the discharging plume. A conceptualization of flow, transport and processes clarified that hydrogeology was the main control on the natural attenuation, as short residence times of 0.5-37 days restricted the time in which dechlorination could occur. This study reveals the importance of: taking an integrated approach to understand the influence of all attenuation processes in groundwater – surface water interactions; considering the scale and domain of interest when determining the main processes; and monitoring sufficiently both spatially and temporally to cover the transient conditions.

Contribution of groundwater discharge and associated contaminants input to Dongting Lake, Central China, using multiple tracers (222Rn, 18O, Cl-).

Lacustrine groundwater discharge (LGD) can play an important role in water and contaminant mass balance of lakes. Dongting Lake is the second largest fresh lake in China which is connected to Yangtze River and has quite prominent ecological status and function within Yangtze River basin. However, the effect of groundwater discharge on the balance of water and contaminant in Dongting Lake has long been overlooked. This study estimated the groundwater discharge and associated contaminants input into Dongting Lake during the dry season using multiple tracers (222Rn, 18O, Cl-). After sensitivity analysis of different models, it is found that the result of 222Rn mass balance model is the most reliable. Based on the 222Rn mass balance model, the groundwater discharge rate is estimated to be 73.94mm/d and the contribution of LGD to water balance is 10.94%. As the main nutrient components, NH3-N, P and Si from groundwater input account for 23.65%, 5.12% and 30.15% % of the total input, respectively. As the main heavy metal components, Fe, Mn and As from groundwater input all account for more than 50% of the total input. Although the LGD rate is relatively small, the contaminant input from LGD is significant enough, which may be a potential threat to the ecological stability of Dongting Lake. In this study, the mass balance models of multiple tracers were integrated to understand the role of groundwater in maintaining the water balance and pollution status of Dongting Lake, which has certain reference significance for the LGD study in plain lakes or reservoirs with complex water systems in humid regions.

Numerical Modeling of Heat and Mass Transport with Inner Heat Exchange in Unsaturated Porous Media

We are focused to the numerical modelling of heat, contaminant and water transport in unsaturated porous media in 3D. The heat exchange between water and porous media matrix is taken into the account. The determination of heat energy transmission coefficient and matrix heat conductivity is solved by means of inverse problem methods. The mathematical model represents the conservation of heat, contaminant and water mass balance. It is expressed by coupled non-linear system of parabolic-elliptic equations. Mathematical model for water transport in unsaturated porous media is represented by Richard's type equation. Heat transport by water includes water flux, molecular diffusion and dispersion. A successful experiment scenario is suggested to determine the required parameters including heat transmission and matrix heat conductivity coefficients. Additionally we investigate contaminant transport with heat transmission and contaminant adsorption. The obtained experiments support our method suitable for solution of direct and inverse problems. This problem we have discussed previously in 1D model, but preferential streamlines in 1D thin tubes shadow accurate results in determination of required parameters. In our presented setting we consider a cylindrical sample which is suitable in laboratory experiments for inverse problems.

Fate and mass balance of contaminants of emerging concern during wastewater treatment determined using the fractionated approach

Contaminants of emerging concern (CECs) are often poorly removed from wastewater using conventional treatment technologies and there is limited understanding of their fate during treatment. Inappropriate sampling strategies lead to inaccuracies in estimating removals of CECs. In this study, we used the “fractionated approach” that accounts for the residence time distribution (RTD) in treatment units to investigate the fate of 26 target CECs in a municipal wastewater treatment plant (WWTP) that includes primary, secondary and tertiary treatment steps. Prior hydraulic calibration of each treatment unit was performed. Wastewater and sludge samples were collected at different locations along the treatment train and the concentrations of target CECs were measured by liquid chromatography mass spectrometry. The most substantial aqueous removal occurred during activated sludge treatment (up to 99%). Removals were <50% in the primary clarifier and tertiary rotating biological contactors (RBCs) and up to 70% by sand filtration. Mass balance calculations demonstrated that (bio)degradation accounted for up to 50% of the removal in the primary clarifier and 100% in activated sludge. Removal by sorption to primary and secondary sludge was minimal for most CECs. Analysis of the selected metabolites demonstrated that negative removals obtained could be explained by transformations between the parent compound and their metabolites. This study contributes to the growing literature by applying the fractionated approach to calculate removal of different types of CECs across each wastewater treatment step. An additional level of understanding of the fate of CECs was provided by mass balance calculations in primary and secondary treatments.

Source Apportionment and Distribution of Polycyclic Aromatic Hydrocarbons, Risk Considerations, and Management Implications for Urban Stormwater Pond Sediments in Minnesota, USA

High concentrations of polycyclic aromatic hydrocarbons (PAHs) are accumulating in many urban stormwater ponds in Minnesota, resulting in either expensive disposal of the excavated sediment or deferred maintenance by economically challenged municipalities. Fifteen stormwater ponds in the Minneapolis-St. Paul, MN, metropolitan area were studied to determine sources of PAHs to bed sediments through the application of several environmental forensic techniques, including a contaminant mass balance receptor model. The model results were quite robust and indicated that coal tar-based sealant (CT-sealant) particulate washoff and dust sources were the most important sources of PAHs (67.1%), followed by vehicle-related sources (29.5%), and pine wood combustion particles (3.4%). The distribution of 34 parent and alkylated PAHs was also evaluated regarding ancillary measurements of black carbon, total organic carbon, and particle size classes. None of these parameters were significantly different based on major land-use classifications (i.e., residential, commercial, and industrial) for pond watersheds. PAH contamination in three stormwater ponds was high enough to present a risk to benthic invertebrates, whereas nine ponds exceeded human health risk-based benchmarks that would prompt more expensive disposal of dredged sediment. The State of Minnesota has been addressing the broader issue of PAH-contaminated stormwater ponds by encouraging local municipalities to ban CT-sealants (29 in all) and to promote pollution prevention alternatives to businesses and homeowners, such as switching to asphalt-based sealants. A statewide CT-sealant ban was recently enacted. Other local and regional jurisdictions may benefit from using Minnesota's approach where CT-sealants are still used.

Mercury in the Mediterranean. Part 2: processes and mass balance

Mass balance of contaminants can provide useful information on the processes that influence their concentrations in various environmental compartments. The most important sources, sinks and the equilibrium or non-equilibrium state of the contaminant in individual environmental compartments can also be identified. Using the latest mercury speciation data, the results of numerical models and the results of recent studies on mercury transport and transformation processes in the marine environment, we have re-evaluated the total mercury (HgT) mass balance in the Mediterranean Sea. New calculations have been performed employing three distinct marine layers: the surface layer, the thermocline and the deep sea. New transport mechanisms, deep water formation and density-driven sinking and upwelling, were included in the mass balance calculations. The most recent data have even enabled the calculation of an approximate methylmercury (MeHg) mass balance. HgT is well balanced in the entire Mediterranean, and the discrepancies between inputs and outputs in individual layers do not exceed 20 %. The MeHg balance shows larger discrepancies between gains and losses due to measurement uncertainties and gaps in our knowledge of Hg species transformation processes. Nonetheless, the main sources and sinks of HgT (deposition and evasion) and MeHg (fluxes from sediment, outflow through the Gibraltar Strait) are in accordance with previous studies on mercury in the Mediterranean Basin. Mercury in the Mediterranean fish harvest is the second largest MeHg sink; about 300 kg of this toxic substance is consumed annually with sea food.

Application of a contaminant mass balance method at an old landfill to assess the impact on water resources

Old and unlined landfill sites pose a risk to groundwater and surface water resources. While landfill leachate plumes in sandy aquifers have been studied, landfills in clay till settings and their impact on receiving water bodies are not well understood. In addition, methods for quantitatively linking soil and groundwater contamination to surface water pollution are required. This paper presents a method which provides an estimate of the contaminant mass discharge, using a combination of a historical investigation and contaminant mass balance approach. The method works at the screening level and could be part of a risk assessment. The study site was Risby Landfill, an old unlined landfill located in a clay till setting on central Zealand, Denmark. The contaminant mass discharge was determined for three common leachate indicators: chloride, dissolved organic carbon and ammonium. For instance, the mass discharge of chloride from the landfill was 9.4ton/year and the mass discharge of chloride to the deep limestone aquifer was 1.4ton/year. This resulted in elevated concentrations of leachate indicators (chloride, dissolved organic carbon and ammonium) in the groundwater. The mass discharge of chloride to the small Risby Stream down gradient of the landfill was approximately 31kg/year. The contaminant mass balance method worked well for chloride and dissolved organic carbon, but the uncertainties were elevated for ammonium due to substantial spatial variability in the source composition and attenuation processes in the underlying clay till.

Global optimization of water networks design using multiparametric disaggregation

We propose new mixed-integer linear programming models for the optimal design of water-using and wastewater treatment networks. These replace the original non-convex, nonlinear problems following parameterization of the concentration variables appearing in the bilinear terms resulting from the contaminant mass balances. The difference between the models lies in the numeric system used for the parameterization. We show how to perform the transformation for a generic coding and give the results for the decimal and binary systems. While the resulting MILPs are approximations of the original NLP, any desired accuracy level can be set, being the proposed models exact in the limit of an infinite number of significant digits. Through the solution of several test cases taken from the literature, we show that the value of the objective function rapidly approaches the global optimal solution. The models can also be used to initialize the NLP when solved with local optimization solvers.

Performance Evaluation Using a Three Compartment Mass Balance for the Removal of Volatile Organic Compounds in Pilot Scale Constructed Wetlands

To perform a general assessment of treatment efficiency, a mass balance study was undertaken for two types of constructed wetlands (CWs), planted gravel filters and plant root mat systems, for treating VOC (benzene; MTBE) polluted groundwater under field conditions. Contaminant fate was investigated in the respective water, plant, and atmosphere compartments by determining water and atmospheric contaminant loads and calculating contaminant plant uptake, thereby allowing for an extended efficiency assessment of CWs. Highest total VOC removal was achieved during summer, being pronounced for benzene compared to MTBE. According to the experimental results and the calculations generated by the balancing model, degradation in the rhizosphere and plant uptake accounted for the main benzene removal processes, of 76% and 13% for the gravel bed CW and 83% and 11% for the root mat system. Volatilization flux of benzene and MTBE was low (<5%) for the gravel bed CW, while in the root mat system direct contact of aqueous and gaseous phases favored total MTBE volatilization (24%). With this applied approach, we present detailed contaminant mass balances that allow for conclusive quantitative estimation of contaminant elimination and distribution processes (e.g., total, surface, and phytovolatilization, plant uptake, rhizodegradation) in CWs under field conditions.

Stochastic modelling of phytoremediation

Leaching of heavy metals and other contaminants from soils poses a significant environmental threat as it affects the quality of downstream water bodies. Quantifying these losses is particularly important when employing phytoremediation approaches to reduce soil contamination, as contaminant escaping the system through leaching cannot be taken up by vegetation. Despite its undoubted importance, the role of such hydrologic forcing has seldom been fully considered in models describing the long-term contaminant mass balance during phytoremediation. The partitioning of contaminants between leaching and vegetation uptake is controlled by a number of biophysical processes as well as rainfall variability. Here, we develop a novel stochastic framework that provides analytical expressions to quantify the partitioning of contaminants between leaching and plant uptake and the probability of phytoremediation duration as a function of rainfall statistics and soil and vegetation characteristics. Simple expressions for the mean phytoremediation duration and effectiveness (defined as the fraction of contaminant that is recovered in plant biomass) are derived. The proposed framework can be employed to estimate under which conditions phytoremediation is more efficient, as well as to design phytoremediation projects that maximize contaminant recovery and minimize the duration of the remediation process.

Mass balance in the monitoring of pollutants in tidal rivers of the Guanabara Bay, Rio de Janeiro, Brazil

This study addressed the identification and monitoring of pollution sources of terrestrial origin in rivers (domestic sewage and industrial effluents) and critical fluvial segments in highly polluted environments under tidal influence (mixing marine and continental sources) from Guanabara Bay Basin, Rio de Janeiro, Brazil. The mass balance of contaminants was determined in conditions of continuous flow (low tide) during dry season (lower dilution capability). The results allowed the evaluation of the potential of contaminant mass generation by the different river segments and the estimation of their natural and anthropogenic components. The water quality of Iguaçú and Sarapuí Rivers were evaluated for metals and biochemical oxygen demand. The method gave an excellent response, including the possibility of sources identification and contaminated river segments ranking. The approach also offers fast execution and data interpretation, being highly efficient.

Mass fluxes of xenobiotics below cities: challenges in urban hydrogeology

Urban areas are the focus of major ecological, social and economical activity. They are thus also prime locations of increasing conflict with regard to water use and water protection. As a direct and/or indirect consequence of urban land use and human activity, urban water systems are frequently polluted with organic contaminants including waste water-born xenobiotics such as pharmaceuticals, personal care products (collectively known as PPCPs) and endocrine-active substances. This study reviews new integrated methodologies including flux calculations as well as chemical investigations for determining the impact of human activities on urban water systems and on processes within the urban watershed. The use of indicator substances, representing different contaminant sources and pathways, integral pumping tests and mass balance approaches are suitable alternatives within these environments. The issues are explored using contaminant mass balance examples from Halle/Saale and Leipzig, Germany.

Micropollutant Loads in the Urban Water Cycle

The assessment of micropollutants in the urban aquatic environment is a challenging task since both the water balance and the contaminant concentrations are characterized by a pronounced variability in time and space. In this study the water balance of a central European urban drainage catchment is quantified for a period of one year. On the basis of a concentration monitoring of several micropollutants, a contaminant mass balance for the study area's wastewater, surface water, and groundwater is derived. The release of micropollutants from the catchment was mainly driven by the discharge of the wastewater treatment plant. However, combined sewer overflows (CSO) released significant loads of caffeine, bisphenol A, and technical 4-nonylphenol. Since an estimated fraction of 9.9-13.0% of the wastewater's dry weather flow was lost as sewer leakages to the groundwater, considerable loads of bisphenol A and technical 4-nonylphenol were also released by the groundwater pathway. The different temporal dynamics of release loads by CSO as an intermittent source and groundwater as well as treated wastewater as continuous pathways may induce acute as well as chronic effects on the receiving aquatic ecosystem. This study points out the importance of the pollution pathway CSO and groundwater for the contamination assessments of urban water resources.

Optimization of Total Networks of Water-Using and Treatment Units by Genetic Algorithms

The optimization of an integrated network of water-using (WU) and treatment (TU) units is addressed in this paper, by targeting for maximum treated water reuse as a considerably better alternative to fresh water consumption. An optimal integrated water network (WN) is an oriented graph, starting with inlet contaminant free WUs and then the other WUs ranked by a certain criteria. The outlet wastewater streams are either split to be reused by the next WUs in sequence or sent to treatment. The mathematical model of the integrated WN is based upon total and contaminant species mass balances for each and every WU/TU which is restricted with respect to the inlet and outlet contaminant concentrations. The performance of the approach is tested on a synthetic example. Several scenarios were used, the results being analyzed in connection with the reduction of fresh water consumption and the increase of internal and treated water reuse.

Performing contaminant mass balances for remedy assessments

AbstractContaminant mass‐balance assessments are useful tools to help quantify various mass transport and removal mechanisms that may be active in a remedial system setting. This article presents the basics of performing a mass balance and illustrates the utility of using the information derived to support project management decisions. It is important to understand the partitioning of contaminant mass into various environmental media and physical forms, as well as the relationships among the partitions. Contaminant partitioning tends toward an equilibrium state, so natural or engineered mass transfer into or out of one partition will affect the others. Mass balances are exercises that quantify, to the extent possible, the contaminant mass in the various environmental partitions and the transfer and transformation processes that affect contaminant distribution. Understanding mass partitioning and transfer mechanisms helps remediation practitioners to engineer and optimize those mechanisms that contribute to risk reduction at a contaminated site. Such knowledge can inform risk managers when natural mechanisms may dominate engineered approaches and help identify uncertainties in contaminant fate and transport. © 2009 Wiley Periodicals, Inc.