Advances in Catchment Science, Hydrochemistry, and Aquatic Ecology Enabled by High-Frequency Water Quality Measurements.

High-frequency water quality measurements in streams and rivers have expanded in scope and sophistication during the last two decades. Existing technology allows in situ automated measurements of water quality constituents, including both solutes and particulates, at unprecedented frequencies from seconds to subdaily sampling intervals. This detailed chemical information can be combined with measurements of hydrological and biogeochemical processes, bringing new insights into the sources, transport pathways, and transformation processes of solutes and particulates in complex catchments and along the aquatic continuum. Here, we summarize established and emerging high-frequency water quality technologies, outline key high-frequency hydrochemical data sets, and review scientific advances in key focus areas enabled by the rapid development of high-frequency water quality measurements in streams and rivers. Finally, we discuss future directions and challenges for using high-frequency water quality measurements to bridge scientific and management gaps by promoting a holistic understanding of freshwater systems and catchment status, health, and function.

Great Lakes Runoff Intercomparison Project Phase 3: Lake Erie (GRIP-E).

Hydrologic model intercomparison studies help to evaluate the agility of models to simulate variables such as streamflow, evaporation, and soil moisture. This study is the third in a sequence of the Great Lakes Runoff Intercomparison Projects. The densely populated Lake Erie watershed studied here is an important international lake that has experienced recent flooding and shoreline erosion alongside excessive nutrient loads that have contributed to lake eutrophication. Understanding the sources and pathways of flows is critical to solve the complex issues facing this watershed. Seventeen hydrologic and land-surface models of different complexity are set up over this domain using the same meteorological forcings, and their simulated streamflows at 46 calibration and seven independent validation stations are compared. Results show that: (1) the good performance of Machine Learning models during calibration decreases significantly in validation due to the limited amount of training data; (2) models calibrated at individual stations perform equally well in validation; and (3) most distributed models calibrated over the entire domain have problems in simulating urban areas but outperform the other models in validation.

Do geographically isolated wetlands influence landscape functions?

Geographically isolated wetlands (GIWs), those surrounded by uplands, exchange materials, energy, and organisms with other elements in hydrological and habitat networks, contributing to landscape functions, such as flow generation, nutrient and sediment retention, and biodiversity support. GIWs constitute most of the wetlands in many North American landscapes, provide a disproportionately large fraction of wetland edges where many functions are enhanced, and form complexes with other water bodies to create spatial and temporal heterogeneity in the timing, flow paths, and magnitude of network connectivity. These attributes signal a critical role for GIWs in sustaining a portfolio of landscape functions, but legal protections remain weak despite preferential loss from many landscapes. GIWs lack persistent surface water connections, but this condition does not imply the absence of hydrological, biogeochemical, and biological exchanges with nearby and downstream waters. Although hydrological and biogeochemical connectivity is often episodic or slow (e.g., via groundwater), hydrologic continuity and limited evaporative solute enrichment suggest both flow generation and solute and sediment retention. Similarly, whereas biological connectivity usually requires overland dispersal, numerous organisms, including many rare or threatened species, use both GIWs and downstream waters at different times or life stages, suggesting that GIWs are critical elements of landscape habitat mosaics. Indeed, weaker hydrologic connectivity with downstream waters and constrained biological connectivity with other landscape elements are precisely what enhances some GIW functions and enables others. Based on analysis of wetland geography and synthesis of wetland functions, we argue that sustaining landscape functions requires conserving the entire continuum of wetland connectivity, including GIWs.

Integrating geographically isolated wetlands into land management decisions.

Wetlands across the globe provide extensive ecosystem services. However, many wetlands - especially those surrounded by uplands, often referred to as geographically isolated wetlands (GIWs) - remain poorly protected. Protection and restoration of wetlands frequently requires information on their hydrologic connectivity to other surface waters, and their cumulative watershed-scale effects. The integration of measurements and models can supply this information. However, the types of measurements and models that should be integrated are dependent on management questions and information compatibility. We summarize the importance of GIWs in watersheds and discuss what wetland connectivity means in both science and management contexts. We then describe the latest tools available to quantify GIW connectivity and explore crucial next steps to enhancing and integrating such tools. These advancements will ensure that appropriate tools are used in GIW decision making and maintaining the important ecosystem services that these wetlands support.

Signatures of human impact: size distributions and spatial organization of wetlands in the Prairie Pothole landscape.

More than 50% of global wetland area has been lost over the last 200 years, resulting in losses of habitat and species diversity as well as decreased hydrologic and biogeochemical functionality. Recognition of the magnitude of wetland loss as well as the wide variety of ecosystem services provided by wetlands has in recent decades led to an increased focus on wetland restoration. Restoration activities, however, often proceed in an ad hoc manner, with a focus on maximizing the total restored area rather than on other spatial attributes of the wetland network, which are less well understood. In this study, we have addressed the question of how human activities have altered the size distribution and spatial organization of wetlands over the Prairie Pothole Region of the Des Moines Lobe using high- resolution LIDAR data. Our results show that as well as the generally accepted 90% loss of depressional wetland area, there has been a preferential loss of smaller wetlands, with a marked alteration of the historical power-law relationship observed between wetland size and frequency and a resulting homogenization of the wetland size distribution. In addition, our results show significant decreases in perimeter-to-area ratios, increased mean distances between wetlands, particularly between smaller wetlands, and a reduced likelihood that current wetlands will, be located in upland areas. Such patterns of loss can lead to disproportionate losses of ecosystem services, as smaller wetlands with larger perimeter-to- area ratios have been found to provide higher rates of biogeochemical processing and groundwater recharge, while increased mean distances between wetlands hinder species migration and thus negatively impact biodiversity. These results suggest the need to gear restoration efforts toward understanding and recreating the size distribution and spatial organization of historical wetlands, rather than focusing primarily on an increase in overall area.

Monsoon harvests: the living legacies of rainwater harvesting systems in South India.

Rainwater harvesting, a "soft path" approach toward water management, is increasingly recognized as a key strategy toward ensuring food security and alleviating problems of water scarcity. Interestingly this "modern" approach has been in use for millennia in numerous older civilizations. This article uses India as a case study to explore the social, economic, and environmental dimensions of agricultural rainwater harvesting ponds, and evaluates the viability of these centuries-old systems under current climate and population pressures. A holistic watershed-scale approach that accounts for trade-offs in water availability and socioeconomic wellbeing is recommended for assessing the sustainability of these systems.

Size and temperature drive nutrient retention potential across water bodies in China.

Lentic water bodies, including lakes, reservoirs, and wetlands, retain excess nutrients in runoff from agricultural and urban activities, and protect downstream water bodies from eutrophication. To develop effective nutrient mitigation strategies, it is important to understand the controls on nutrient retention in lentic systems and what drives variability between different systems and geographical regions. Efforts to synthesize water body nutrient retention at the global scale are biased toward studies from North America and Europe. Numerous studies published in Chinese Language journals exist in the extensive China National Knowledge Infrastructure (CNKI), but are missing from global synthesis due to their absence in English language journal databases. We address this gap by synthesizing data from 417 waterbodies in China to assess hydrologic and biogeochemical drivers of nutrient retention. In this study, we found median retention of 46 and 51% for nitrogen and phosphorus, respectively, across all water bodies in our national synthesis, and on average, wetlands retain more nutrients than lakes or reservoirs. The analysis of this dataset highlights the influence of water body size on first-order nutrient removal rate constants, as well as how regional temperature variations affect nutrient retention in water bodies. The dataset was used to calibrate the HydroBio-k model, which explicitly considers the effect of residence times and temperature on nutrient retention. Application of the HydroBio-k model across China reveals patterns of nutrient removal potential, where regions with a higher density of small water bodies retain more nutrients than others, such that regions like the Yangtze River Basin with a greater proportion of smaller water bodies have greater retention rates. Our results emphasize the importance of lentic systems and their function in nutrient removal and water quality improvement, as well as the drivers and variability of these functions at the landscape scale.

Seasonality of inundation in geographically isolated wetlands across the United States.

Inundation area is a major control on the ecosystem services provisioned by geographically isolated wetlands. Despite its importance, there has not been any comprehensive study to map out the seasonal inundation characteristics of geographically isolated wetlands over the continental United States (CONUS). This study fills the aforementioned gap by evaluating the seasonality or the long-term intra-annual variations of wetland inundation in ten wetlandscapes across the CONUS. We also assess the consistency of these intra-annual variations. Finally, we evaluate the extent to which the seasonality can be explained based on widely available hydrologic fluxes. Our findings highlight significant intra-annual variations of inundation within most wetlandscapes, with a standard deviation of the long-term averaged monthly inundation area ranging from 15% to 151% of its mean across the wetlandscapes. Stark differences in inundation seasonality are observed between snow-affected vs. rain-fed wetlandscapes. The former usually shows the maximum monthly inundation in April following spring snowmelt (SM), while the latter experiences the maximum in February. Although the magnitude of inundation fraction has changed over time in several wetlandscapes, the seasonality of these wetlands shows remarkable constancy. Overall, commonly available regional hydrologic fluxes (e.g. rainfall, SM, and evapotranspiration) are found to be able to explain the inundation seasonality at wetlandscape scale with determination coefficients greater than 0.57 in 7 out of 10 wetlandscapes. Our methodology and presented results may be used to map inundation seasonality and consequently account for its impact on wetland functions.

Long-term annual soil nitrogen surplus across Europe (1850-2019).

Worldwide surface waters suffer from the presence of nitrogen (N) compounds causing eutrophication and deterioration of the water quality. Despite many Europe-wide legislation's, we still observe high N levels across many water bodies in Europe. Information on long-term annual soil N surplus is needed to better understand these N levels and inform future management strategies. Here, we reconstructed and analysed the annual long-term N surplus for both agricultural and non-agricultural soils across Europe at a 5 arcmin (≈10 km at the equator) spatial resolution for more than a century (1850-2019). The dataset consists of 16 N surplus estimates that account for the uncertainties resulting from input data sources and methodological choices in major components of the N surplus. We documented the consistency and plausibility of our estimates by comparing them with previous studies and discussed about possible avenues for further improvements. Importantly, our dataset offers the flexibility of aggregating the N surplus at any spatial scale of relevance to support water and land management strategies.

Nitrogen legacies in anthropogenic landscapes: a case study in the Mondego Basin in Portugal.

Nitrogen (N) legacies have built up in anthropogenic landscapes over decades of agricultural intensification, and these legacies lead to time lags in water quality change measurable even beyond the moment of application of N. It is important to understand these legacies to quantify the relationship between N inputs and N concentrations in streams and implement best management practices for water quality improvement; however, little is known about the magnitude of legacies in various landscape elements like soils and groundwater. Here, we have used the ELEMeNT (Exploration of Long-tErM Nutrient Trajectories) model to explore the buildup and depletion of N legacies over a 216-year period, across the Mondego River Basin, a 6645-km2 watershed in Portugal, where human interventions have considerably changed the characteristics of the basin to prevent floods and improve farming conditions in recent decades. The results show that the increase in the amount of inorganic fertilizer applied was the main driver for the anthropogenic N loads in the watershed from 1950 until the beginning of the 1990s. The N inputs have been decreasing since then, but N loads in the river did not document any decrease till the 1990s; after which there was a decline. This time lag between the N inputs to the watershed and the N loads in the river (about two decades) is a function of accumulation of N legacy.

Agricultural phosphorus surplus trajectories for Ontario, Canada (1961-2016), and erosional export risk.

Management strategies aimed at reducing nutrient enrichment of surface waters may be hampered by nutrient legacies that have accumulated in the landscape. Here, we apply the Net Anthropogenic Phosphorus Input (NAPI) model to reconstruct the historical phosphorus (P) input trajectories for the province of Ontario, which encompasses the Canadian portion of the drainage basin of the Laurentian Great Lakes (LGL). NAPI considers P inputs from detergent, human and livestock waste, fertilizer inputs, and P outputs by crop uptake. During the entire time period considered, from 1961 to 2016, Ontario experienced positive annual NAPI values. Despite a generally downward NAPI trend since the late 1970s, the lower LGL, especially Lake Erie, continue to be plagued by algal blooms. When comparing NAPI results and river monitoring data for the period 2003 to 2013, P discharged by Canadian rivers into Lake Erie only accounts for 12.5% of the NAPI supplied to the watersheds' agricultural areas. Thus, over 85% of the agricultural NAPI is retained in the watersheds where it contributes to a growing P legacy, primarily as soil P. The slow release of legacy P therefore represents a long-term risk to the recovery of the lake. To help mitigate this risk, we present a methodology to spatially map out the source areas with the greatest potential of erosional export of legacy soil P to surface waters. These areas should be prioritized in soil conservation efforts.

Vulnerable Waters are Essential to Watershed Resilience.

Watershed resilience is the ability of a watershed to maintain its characteristic system state while concurrently resisting, adapting to, and reorganizing after hydrological (for example, drought, flooding) or biogeochemical (for example, excessive nutrient) disturbances. Vulnerable waters include non-floodplain wetlands and headwater streams, abundant watershed components representing the most distal extent of the freshwater aquatic network. Vulnerable waters are hydrologically dynamic and biogeochemically reactive aquatic systems, storing, processing, and releasing water and entrained (that is, dissolved and particulate) materials along expanding and contracting aquatic networks. The hydrological and biogeochemical functions emerging from these processes affect the magnitude, frequency, timing, duration, storage, and rate of change of material and energy fluxes among watershed components and to downstream waters, thereby maintaining watershed states and imparting watershed resilience. We present here a conceptual framework for understanding how vulnerable waters confer watershed resilience. We demonstrate how individual and cumulative vulnerable-water modifications (for example, reduced extent, altered connectivity) affect watershed-scale hydrological and biogeochemical disturbance response and recovery, which decreases watershed resilience and can trigger transitions across thresholds to alternative watershed states (for example, states conducive to increased flood frequency or nutrient concentrations). We subsequently describe how resilient watersheds require spatial heterogeneity and temporal variability in hydrological and biogeochemical interactions between terrestrial systems and down-gradient waters, which necessitates attention to the conservation and restoration of vulnerable waters and their downstream connectivity gradients. To conclude, we provide actionable principles for resilient watersheds and articulate research needs to further watershed resilience science and vulnerable-water management.

The need to integrate legacy nitrogen storage dynamics and time lags into policy and practice.

Increased fluxes of reactive nitrogen (Nr), often associated with N fertilizer use in agriculture, have resulted in negative environmental consequences, including eutrophication, which cost billions of dollars per year globally. To address this, best management practices (BMPs) to reduce Nr loading to the environment have been introduced in many locations. However, improvements in water quality associated with BMP implementation have not always been realised over expected timescales. There is a now a significant body of scientific evidence showing that the dynamics of legacy Nr storage and associated time lags invalidate the assumptions of many models used by policymakers for decision making regarding Nr BMPs. Building on this evidence, we believe that the concepts of legacy Nr storage dynamics and time lags need to be included in these models. We believe the biogeochemical research community could play a more proactive role in advocating for this change through both awareness raising and direct collaboration with policymakers to develop improved datasets and models. We anticipate that this will result in more realistic expectations of timescales for water quality improvements associated with BMPs. Given the need for multi-nutrient policy responses to tackle challenges such as eutrophication, integration of N stores will have the further benefit of aligning both researchers and policymakers in the N community with the phosphorus and carbon communities, where estimation of stores is more widespread. Ultimately, we anticipate that integrating legacy Nr storage dynamics and time lags into policy frameworks will better meet the needs of human and environmental health.

Turnover and legacy of sediment-associated PAH in a baseflow-dominated river.

Polycyclic Aromatic Hydrocarbons (PAH) ubiquitously occur in rivers and threaten the aquatic ecosystem. Understanding their fate and behaviour in rivers can help in improving management strategies. We develop a particle-facilitated transport model considering suspended sediments with sorbed PAH from different origins to investigate the turnover and legacy of sediment-bound PAH in the baseflow-dominated Ammer River in southwest Germany. Our model identifies the contributions of dissolved and particle-bound PAH during wet and dry periods to the annual load. The analysis of in-stream processes enables investigating the average turnover times of sediments and attached PAH for the main stem of the river. The legacy of sediment-bound PAH is studied by running the model assuming a 50% reduction in PAH emissions after the introduction of environmental regulation in the 1970s. Our results show that sediment-bound and dissolved PAH account for 75% and 25% of the annual PAH load, respectively. PAH are mainly emitted from urban areas that contribute over 74% to the total load. In steep reaches, the turnover times of sediments and attached PAH are similar, whereas they differ by 1-2 orders of magnitude in reaches with very mild slopes. Flow rates significantly affect PAH fluxes between the mobile water and the riverbed over the entire river. Total PAH fluxes from the river bed to the mobile water are simulated to occur when the discharge is larger than 5 m3s -1. River segments with large sediment storage show a potential of PAH legacy, which may have caused a PAH release over 10-20 years after the implementation of environmental regulation. This study is useful for assessing environmental impacts of PAH in rivers (e.g., their contribution to the river-water toxicity) and exemplifies that the longitudinal distribution, turnover, and legacy potential of PAH in a river system require a mechanistic understanding of river hydraulics and sediment transport.

Simplified contaminant source depletion models as analogs of multiphase simulators.

Four simplified dense non-aqueous phase liquid (DNAPL) source depletion models recently introduced in the literature are evaluated for the prediction of long-term effects of source depletion under natural gradient flow. These models are simple in form (a power function equation is an example) but are shown here to serve as mathematical analogs to complex multiphase flow and transport simulators. The spill and subsequent dissolution of DNAPLs was simulated in domains having different hydrologic characteristics (variance of the log conductivity field=0.2, 1 and 3) using the multiphase flow and transport simulator UTCHEM. The dissolution profiles were fitted using four analytical models: the equilibrium streamtube model (ESM), the advection dispersion model (ADM), the power law model (PLM) and the Damkohler number model (DaM). All four models, though very different in their conceptualization, include two basic parameters that describe the mean DNAPL mass and the joint variability in the velocity and DNAPL distributions. The variability parameter was observed to be strongly correlated with the variance of the log conductivity field in the ESM and ADM but weakly correlated in the PLM and DaM. The DaM also includes a third parameter that describes the effect of rate-limited dissolution, but here this parameter was held constant as the numerical simulations were found to be insensitive to local-scale mass transfer. All four models were able to emulate the characteristics of the dissolution profiles generated from the complex numerical simulator, but the one-parameter PLM fits were the poorest, especially for the low heterogeneity case.

Temporal evolution of DNAPL source and contaminant flux distribution: impacts of source mass depletion.

We investigated, using model simulations, the changes occurring in the distribution of dense non-aqueous phase liquid (DNAPL) mass (Sn) within the source zone during depletion through dissolution, and the resulting changes in the contaminant flux distribution (J) at the source control plane (CP). Two numerical codes (ISCO3D and T2VOC) were used to simulate selected scenarios of DNAPL dissolution and transport in three-dimensional, heterogeneous, spatially correlated, random permeability fields with emplaced sources. Data from the model simulations were interpreted based on population statistics (mean, standard deviation, coefficient of variation) and spatial statistics (centroid, second moments, variograms). The mean and standard deviation of the Sn and J distributions decreased with source mass depletion by dissolution. The decrease in mean and standard deviation was proportional for the J distribution resulting in a constant coefficient of variation (CV), while for the Sn distribution, the mean decreased faster than the standard deviation. The spatial distributions exhibited similar behavior as the population distribution, i.e., the CP flux distribution was more stable (defined by temporally constant second moments and range of variograms) than the Sn distribution. These observations appeared to be independent of the heterogeneity of the permeability (k) field (variance of the log permeability field=1 and 2.45), correlation structure (positive vs. negative correlation between the k and Sn domains) and the DNAPL dissolution model (equilibrium vs. rate-limited), for the cases studied. Analysis of data from a flux monitoring field study (Hill Air Force Base, Utah) at a DNAPL source CP before and after source remediation also revealed temporal invariance of the contaminant flux distribution. These modeling and field observations suggest that the temporal evolution of the contaminant flux distribution can be estimated if the initial distribution is known. However, the findings are preliminary and broader implications to sampling strategies for remediation performance assessment need to be evaluated in additional modeling and experimental studies.

Laboratory investigation of flux reduction from dense non-aqueous phase liquid (DNAPL) partial source zone remediation by enhanced dissolution.

This study investigated the benefits of partial removal of dense nonaqueous phase liquid (DNAPL) source zones using enhanced dissolution in eight laboratory scale experiments. The benefits were assessed by characterizing the relationship between reductions in DNAPL mass and the corresponding reduction in contaminant mass flux. Four flushing agents were evaluated in eight controlled laboratory experiments to examine the effects of displacement fluid property contrasts and associated override and underride on contaminant flux reduction (R(j)) vs. mass reduction (R(m)) relationships (R(j)(R(m))): 1) 50% ethanol/50% water (less dense than water), 2) 40% ethyl-lactate/60% water (more dense than water), 3) 18% ethanol/26% ethyl-lactate/56% water (neutrally buoyant), and 4) 2% Tween-80 surfactant (also neutrally buoyant). For each DNAPL architecture evaluated, replicate experiments were conducted where source zone dissolution was conducted with a single flushing event to remove most of the DNAPL from the system, and with multiple shorter-duration floods to determine the path of the R(j)(R(m)) relationship. All of the single-flushing experiments exhibited similar R(j)(R(m)) relationships indicating that override and underride effects associated with cosolvents did not significantly affect the remediation performance of the agents. The R(j)(R(m)) relationship of the multiple injection experiments for the cosolvents with a density contrast with water tended to be less desirable in the sense that there was less R(j) for a given R(m). UTCHEM simulations supported the observations from the laboratory experiments and demonstrated the capability of this model to predict R(j)(R(m)) relationships for non-uniformly distributed NAPL sources.

Evaluation of simplified mass transfer models to simulate the impacts of source zone architecture on nonaqueous phase liquid dissolution in heterogeneous porous media.

Nonaqueous phase liquid (NAPL) dissolution was studied in three-dimensional (3D) heterogeneous experimental aquifers (25.5 cm x 9 cm x 8.5 cm) with two different longitudinal correlation lengths (2.1 cm and 1.1 cm) and initial spill volumes (22.5 ml and 10.5 ml). Spatial and temporal distributions of NAPL during dissolution were measured using magnetic resonance imaging (MRI). At high NAPL spill volume, average effluent concentrations initially increased during dissolution, as NAPL pools transitioned to NAPL ganglia, and then decreased as the total NAPL-water interfacial area decreased over time. Experimental results were used to test six dissolution models: (i and ii) a one-dimensional (1D) model using either specific NAPL-water interfacial area values estimated from MR images at each time step (i.e., 1D quasi-steady state model), or an empirical mass transfer (Sh') correlation (i.e., 1D transient model), (iii and iv) a multiple analytical source superposition technique (MASST) using either the NAPL distribution determined from MR images at each time step (i.e., MASST steady state model), or the NAPL distribution determined from mass balance calculations (i.e., MASST transient model), (v) an equilibrium streamtube model, and (vi) a 3D grid-scale pool dissolution model (PDM) with a dispersive mass flux term. The 1D quasi-steady state model and 3D PDM captured effluent concentration values most closely, including some concentration fluctuations due to changes in the extent of flow reduction. The 1D transient, MASST steady state and transient, and streamtube models all showed a monotonic decrease in effluent concentration values over time, and the streamtube model was the most computationally efficient. Changes during dissolution of the effective NAPL-water interfacial area estimated from imaging data are similar to changes in effluent concentration values. The 1D steady state model incorporates estimates of the effective NAPL-water interfacial area directly at each time point; the 3D PDM does so indirectly through mass balance and a relative permeability function, which causes reduced water flow through high saturation NAPL regions. Hence, when model accuracy is required, the results indicate that a surrogate of this effective interfacial area is required. Approaches to include this surrogate in the MASST and streamtube models are recommended.

Enhancing protection for vulnerable waters.

Governments worldwide do not adequately protect their limited freshwater systems and therefore place freshwater functions and attendant ecosystem services at risk. The best available scientific evidence compels enhanced protections for freshwater systems, especially for impermanent streams and wetlands outside of floodplains that are particularly vulnerable to alteration or destruction. New approaches to freshwater sustainability - implemented through scientifically informed adaptive management - are required to protect freshwater systems through periods of changing societal needs. One such approach introduced in the US in 2015 is the Clean Water Rule, which clarified the jurisdictional scope for federally protected waters. However, within hours of its implementation litigants convinced the US Court of Appeals for the Sixth Circuit to stay the rule, and the subsequently elected administration has now placed it under review for potential revision or rescission. Regardless of its outcome at the federal level, policy and management discussions initiated by the propagation of this rare rulemaking event have potential far-reaching implications at all levels of government across the US and worldwide. At this timely juncture, we provide a scientific rationale and three policy options for all levels of government to meaningfully enhance protection of these vulnerable waters. A fourth option, a 'do-nothing' approach, is wholly inconsistent with the well-established scientific evidence of the importance of these vulnerable waters.

Flux-based assessment at a manufacturing site contaminated with trichloroethylene.

Groundwater and contaminant fluxes were measured, using the passive flux meter (PFM) technique, in wells along a longitudinal transect passing approximately through the centerline of a trichloroethylene (TCE) plume at a former manufacturing plant located in the Midwestern US. Two distinct zones of hydraulic conductivity were identified from the measured groundwater fluxes; a 6-m-thick upper zone ( approximately 7 m to 13 m below the ground surface or bgs) with a geometric mean Darcy flux (q(0)) of 2 cm/day, and a lower zone ( approximately 13 m to 16.5m bgs) with a q(0) approximately 15 cm/day; this important hydrogeologic feature significantly impacts any remediation technology used at the site. The flux-averaged TCE concentrations estimated from the PFM results compared well with existing groundwater monitoring data. It was estimated that at least 800 kg of TCE was present in the source zone. The TCE mass discharge across the source control plane (85 m x 38 m) was used to estimate the "source strength" ( approximately 365 g/day), while mass discharges across multiple down-gradient control planes were used to estimate the plume-averaged, TCE degradation rate constant (0.52 year(-1)). This is close to the rate estimated using the conventional centerline approach (0.78 year(-1)). The mass discharge approach provides a more robust and representative estimate than the centerline approach since the latter uses only data from wells along the plume centerline while the former uses all wells in the plume.