Modelling temporal and spatial changes of PCBs in fish tissue from Lake Huron

A model has been developed to assess temporal and spatial changes in the concentration of polychlorinated biphenyl (PCB) contaminant in whole fish from Lake Huron during the years 1980 to 2004. The model uses log PCB concentration as the response variable and includes time trend, within-lake variability and dependence on age, weight and length as explanatory variables. A preliminary examination of the data revealed that some values are recorded as below detection limits (thus leading to the left censoring), and the PCB concentration appears to show declines in latter years. To this end, parametric log-location-scale regression models used in survival analysis were employed. It has been found that the Weibull model yields a better fit than the log-logistic or the log-normal models. The analysis provides strong evidence that, starting in 1996, the level of PCB concentration showed steady decline, which is most contributed by the Canadian and US governments?? actions carried out earlier to reduce the load of toxic contaminants to the Great Lakes. Spatially, fish from the north of the lake is less contaminated than fish from the south. The pattern and magnitude of the estimated spatial and temporal trends can provide useful information regarding the safety of fish consumption, the setting of regularity limits, the identifiability of PCB sources and the effects of remedial actions in the future. In addition, the developed model is not restricted to the current application but could be used for the analysis of other contaminants.     

Estimating contaminant attenuation half-lives in alluvial groundwater systems

One aspect of describing contamination in an alluvial aquifer is estimating changes in concentrations over time. A variety of statistical methods are available for assessing trends in contaminant concentrations. We present a method that extends trend analysis to include estimating the coefficients for the exponential decay equation and calculating contaminant attenuation half-lives. The conceptual model for this approach assumes that the rate of decline is proportional to the contaminant concentration in an aquifer. Consequently, the amount of time to remove a unit quantity of the contaminant inventory from an aquifer lengthens as the concentration decreases. Support for this conceptual model is demonstrated empirically with log-transformed time series of contaminant data. Equations are provided for calculating system attenuation half-lives for non-radioactive contaminants. For radioactive contaminants, the system attenuation half-life is partitioned into the intrinsic radioactive decay and the concentration reduction caused by aquifer processes. Examples are presented that provide the details of this approach. In addition to gaining an understanding of aquifer characteristics and changes in constituent concentrations, this method can be used to assess compliance with regulatory standards and to estimate the time to compliance when natural attenuation is being considered as a remediation strategy. A special application of this method is also provided that estimates the half-life of the residence time for groundwater in the aquifer by estimating the half life for a conservative contaminant that is no longer being released into the aquifer. Finally, the ratio of the half-life for groundwater residence time to the attenuation half-life for a contaminant is discussed as a system-scale retardation factor which can be used in analytical and numerical modeling.     

Estimating aquatic toxicity as determined through laboratory tests of great lakes sediments containing complex mixtures of environmental contaminants

We developed and evaluated a total toxic units modeling approach for predicting mean toxicity as measured in laboratory tests for Great Lakes sediments containing complex mixtures of environmental contaminants (e.g., polychlorinated biphenyls, polycyclic aromatic hydrocarbons, pesticides, chlorinated dioxins, and metals). The approach incorporates equilibrium partitioning and organic carbon control of bioavailability for organic contaminants and acid volatile sulfide (AVS) control for metals, and includes toxic equivalency for planar organic chemicals. A toxic unit is defined as the ratio of the estimated pore-water concentration of a contaminant to the chronic toxicity of that contaminant, as estimated by U.S. Environmental Protection Agency Ambient Water Quality Criteria (AWQC). The toxic unit models we developed assume complete additivity of contaminant effects, are completely mechanistic in form, and were evaluated without any a posteriori modification of either the models or the data from which the models were developed and against which they were tested. A linear relationship between total toxic units, which included toxicity attributable to both iron and un-ionized ammonia, accounted for about 88% of observed variability in mean toxicity; a quadratic relationship accounted for almost 94%. Exclusion of either bioavailability components (i.e., equilibrium partitioning control of organic contaminants and AVS control of metals) or iron from the model substantially decreased its ability to predict mean toxicity. A model based solely on un-ionized ammonia accounted for about 47% of the variability in mean toxicity. We found the toxic unit approach to be a viable method for assessing and ranking the relative potential toxicity of contaminated sediments.The U.S. Government right to retain a non-exclusive royalty free licence in and to any copyright is acknowledged.     

Dioxin uptake by Indian plant species

Dioxins like various gaseous pollutants and aerosols can be scavenged by appropriate vegetative greenbelts. Based on their stomatal properties and the models for contaminant uptake, uptake of dioxin (2,3,7,8-TCDD) by three important Indian plant species, viz. Eugenia jambolana (Jamun), Azadirachta indica (Neem) and Ficus religiosa (Peepal), has been estimated. 2,3,7,8-TCDD is a contaminant with severe harmful ecological ramifications. Computations show that Ficus religiosa has highest uptake capacity. The present exercise has its utility in designing appropriate green-belts for mitigating adverse environmental and human health impacts due to dioxins. This can be an effective management option for mitigating the damages caused by dioxins.     

RISK ASSESSMENT METHODOLOGY FOR KARST AQUIFERS: (1) ESTIMATING KARST CONDUIT-FLOW PARAMETERS

Quantitative ground-water tracing of conduit-dominated karst aquifers allows for reliable and practical interpretation of karst ground-water flow. Insights into the hydraulic geometry of the karst aquifer may be acquired that otherwise could not be obtained by such conventional methods as potentiometric-surface mapping and aquifer testing. Contamination of karst aquifers requires that a comprehensive tracer budget be performed so that karst conduit hydraulic-flow and geometric parameters be obtained. Acquisition of these parameters is necessary for estimating contaminant fate-and-transport. A FORTRAN computer program for estimating total tracer recovery from tracer-breakthrough curves is proposed as a standard method. Estimated hydraulic-flow parameters include mean residence time, mean flow velocity, longitudinal dispersivity, Peclet number, Reynolds number, and Froude number. Estimated geometric parameters include karst conduit sinuous distance, conduit volume, cross-sectional area, diameter, and hydraulic depth. These parameters may be used to (1) develop structural models of the aquifer, (2) improve aquifer resource management, (3) improve ground-water monitoring systems design, (4) improve aquifer remediation, and (5) assess contaminant fate-and-transport. A companion paper demonstrates the use of these hydraulic-flow and geometric parameters in a surface-water model for estimating contaminant fate-and-transport in a karst conduit. Two ground-water tracing studies demonstrate the utility of this program for reliable estimation of necessary karst conduit hydraulic-flow and geometric parameters.     

A statistical F test for the natural attenuation of contaminants in groundwater

Natural attenuation (NA) is a catchall explanation for the overall decay and slowed movement of the contaminants in the subsurface. One direct support to NA is to demonstrate that contaminant concentrations from monitoring wells located near the source are decreasing over time. The decrease is summarily expressed in terms of an apparent half-life that is determinedfrom the line best fitting the observed log-transformed concentration data and time. This simple (time-only) decay modelassumes other factors are invariant, and so is flawed when complicating factors – such as a fluctuating water table – are present. A history of the water-table fluctuation can track changes in important NA factors like recharge, groundwater flow direction and velocity, as well as other non-NA factors like volume of water in and purged from the well before a sample is collected. When the trend in the concentrations is better associated with the water table rising or falling, any conclusionabout degradation rate may be premature. We develop simple regressions to predict contaminant concentration (c) by two line models: one involving time (c c(t)), and another involving groundwater elevation (c c(z)). We develop a third model that includesboth factors (c c(t, z)). Using an F-test to compare the fits to the models, we determine which modelis statistically better in explaining the observed concentrations. We applied the test to sites where benzene degradation rates had previously been estimated. The F-testcan be used to determine the suitability of applying non-parametric statistics, like the Mann-Kendall, to the concentration data, because the result from the F-test canindicate instability of the contaminant plume that may bemasked when the water table fluctuates.     

A method for monitoring ground water quality near waste storage facilities

A practical optimization approach developed in this paper derives effective monitoring configurations for detecting contaminants in ground water. The approach integrates numerical simulation of contaminant transport and mathematical programming. Well sites identified by the methodology can be monitored to establish the occurrence of a contaminant release before a plume migrates to a regulatory compliance boundary. Monitoring sites are established along several horizons located between the downgradient margin of a contaminant source and a compliance boundary. A horizon can form an effective line of defense against contaminant migration to the compliance boundary if it is spanned (covered) by a sufficient number of sites to yield a well spacing that is equal to or less than a maximum value established by numerical modeling. The objective function of the integer programming model formulation expresses the goals of: (1) covering a maximum number of siting horizons, and (2) allocating wells to the single most effective horizon. The latter is determined from well spacing requirements and the width of the zone of potential contaminant migration traversed by the horizon. The methodology employs a highly tractable linear programming model formulation, and the user is not required to predefine a set of potential well sites. These attributes can facilitate its implementation in practice.     

Some considerations on the use of simple box models of contaminant fate in soils

A simple box model computing time-averaged concentrations in soil and water of contaminants such as pesticides, following a pulse emission under the assumption of constant removal rates, is presented and evaluated against a benchmark model and some lysimeter experiments representative of different soil and climate settings in Europe. The simple box model allows capturing to some extent the trends of contaminant releases observed from lysimeters or predicted by the benchmark model. This suggests that the correct order of magnitude of environmental concentrations and loads of contaminants can be described as a first approximation by a very simple back-of-the-envelope calculation. In the calculation, the time lag between contaminant application and the start of runoff or leaching should be considered. In the absence of more detailed information, repeating the calculation for the extreme cases of zero and one month lag yields a reasonably realistic range, and the geometric mean of the two is suggested as a first guess estimate. This configures a practical approach for the screening of contaminant losses especially suited for the mapping of predicted environmental concentrations (PECs) for assessment at broad scale (such as continental Europe, a country or a large catchment), where contingent determinants of contaminant fate tend to be averaged out and use of more detailed models usually promises to yield little improvement of PECs.     

Uncertainty based optimal monitoring network design for a chlorinated hydrocarbon contaminated site

An application of a newly developed optimal monitoring network for the delineation of contaminants in groundwater is demonstrated in this study. Designing a monitoring network in an optimal manner helps to delineate the contaminant plume with a minimum number of monitoring wells at optimal locations at a contaminated site. The basic principle used in this study is that the wells are installed where the measurement uncertainties are minimum at the potential monitoring locations. The development of the optimal monitoring network is based on the utilization of contaminant concentration data from an existing initial arbitrary monitoring network. The concentrations at the locations that were not sampled in the study area are estimated using geostatistical tools. The uncertainty in estimating the contaminant concentrations at such locations is used as design criteria for the optimal monitoring network. The uncertainty in the study area was quantified by using the concentration estimation variances at all the potential monitoring locations. The objective function for the monitoring network design minimizes the spatial concentration estimation variances at all potential monitoring well locations where a monitoring well is not to be installed as per the design criteria. In the proposed methodology, the optimal monitoring network is designed for the current management period and the contaminant concentration data estimated at the potential observation locations are then used as the input to the network design model. The optimal monitoring network is designed for the consideration of two different cases by assuming different initial arbitrary existing data. Three different scenarios depending on the limit of the maximum number of monitoring wells that can be allowed at any period are considered for each case. In order to estimate the efficiency of the developed optimal monitoring networks, mass estimation errors are compared for all the three different scenarios of the two different cases. The developed methodology is useful in coming up with an optimal number of monitoring wells within the budgetary limitations. The methodology also addresses the issue of redundancy, as it refines the existing monitoring network without losing much information of the network. The concept of uncertainty-based network design model is useful in various stages of a potentially contaminated site management such as delineation of contaminant plume and long-term monitoring of the remediation process.     

An investigation of heavy metal and migration through groundwater from the landfill area of Eskisehir in Turkey

This paper was conducted in order to determine the groundwater and soil pollution within and around the landfill of Eskisehir, Turkey. In this paper, mud, leachate and groundwater samples were collected seasonally a year from near Eskisehir landfill-site to investigate the possible impact of leachate which affects soil and groundwater quality. Concentrations of various heavy metals (Fe, Cu, Zn, Mn, Co, Pb, Cr, Ni and Mo) were determined in mud, leachate and groundwater samples. In addition, the heavy metal transportation infiltrated from landfill through a porous medium into the groundwater was modelled in order to determine the potential groundwater pollution caused by the leachate of the landfill. The modelling of the contaminant transportation was carried out by using a multiflow computer programme which simulates the distribution of heavy metal concentrations. As a result of this study, the distribution of the contaminant concentration was modelled and determined with respect to time and distance. Hence, the contaminant concentrations were determined at any time interval according to distance. The heavy metal contamination in groundwater does not affect the wells found at far points from the source in a short time, e.g. 10, 20 and 30 days according to the obtained experimental results. When the time intervals extended more than 1 year, heavy metal concentrations decrease with distance but the concentration of the contamination increases when it gets closer to the pollution source. In this study, the potential contamination of groundwater was effectively estimated.     

A generalized analytical solution for turbulent dispersion with inhomogeneous wind and diffusion coefficient

A technique is presented to solve analytically the turbulent diffusion equation for the concentration of a passive contaminant emitted from an elevated continuous source into the atmosphere. A generalized method of solution using Sturm–Liouville and WKB theories is developed to overcome difficulties due to the height‐dependent wind velocity and diffusion coefficient appearing in the diffusion equation. The method presented in this paper is able to derive an asymptotic expression for the concentration obtained from the solution of the atmospheric diffusion equation which involves explicitly inhomogeneous wind velocity and diffusion coefficient. The diffusion equation model derived from this method can be applied in a practical prediction of contaminant concentration in a turbulent atmosphere. This revised version was published online in August 2006 with corrections to the Cover Date.     

Comparison of field-observed and model-predicted plume trends at fuel-contaminated sites: implications for natural attenuation rates

Subsequent to modeling of natural attenuation processes to predict contaminant trends and plume dynamics, monitoring data were used to evaluate the effectiveness of natural attenuation at reducing contaminant concentrations in groundwater at seven fuel-contaminated sites. Predicted and observed contaminant trends at seven sites were compared in order to empirically assess the accuracy of some fundamental model input parameters and assumptions. Most of the models developed for the study sites tended to overestimate plume migration distance, source persistence, and/or the time required for the benzene, toluene, ethyl benzene, and xylenes (BTEX) plumes to attenuate. Discrepancies between observed and predicted contaminant trends and plume behavior suggested that the influence of natural attenuation process may not have been accurately simulated. The conservatism of model simulations may be attributed to underestimation of natural source weathering rates, overestimation of the mass of contaminant present in the source area, and/or use of overly conservative first-order solute decay rates.     

Modeling the flow and leachate transport in the vadose and saturated zones of a municipal landfill

The purpose of the present study was to evaluate the groundwater contamination due to the construction and operation of the municipal landfill of Amari, Rethymno, Crete. The groundwater flow and leachate transport in the vadose and saturated zones were studied and simulated, using three different models: the one-dimensional groundwater flow and contaminant transport model for the vadose zone Pesticide Root Zone Model (PRZM-3), the Geographical Information System (GIS) Argus ONE and the three-dimensional groundwater flow and contaminant transport model Princeton Transport Code (PTC). The simulation time was 30 and 20 years, and the results obtained, according to the models and the existing hydrogeological conditions, were very encouraging and reassuring about the groundwater quality of the broad region.     

Historical contamination of the Anacostia River, Washington, D.C.

The tidal Anacostia River in Washington DC has long been impacted by various sources of chemical pollution over the past 200 years. To explore more recent inputs of various chemicals, six sediment cores were collected for dating and chemical analysis in the downstream section of the tidal Anacostia River. Profiles of contaminants in sediment cores can be useful in determining management direction and effectiveness of pollution controls over time. There were two main objectives for this investigation: (1) determine current sediment contaminant levels; (2) determine a historical perspective of the sediment changes in contamination using (137)Cs and (210)Pb dating. The determination of an age-depth relationship using (210)Pb and (137)Cs dating gave somewhat different results, suggesting that the assumptions of (210)Pb dating were not met. Using the (137)Cs horizon allowed an assignment of approximate sediment accumulation rates and hence an age-depth relationship to contaminant events in the upper portions of the cores. Total PAHs showed higher concentrations at depth and lower surface concentrations. In the upper sections, PAHs were a mixture of combustion and petrogenic sources, while at depth the signature appeared to be of natural origins. Total PCBs, DDTs and chlordane concentrations showed a maximum in recent sediments, decreasing towards the surface. PCBs had lower molecular weight congeners near the surface and higher molecular weights at depth. A phthalate ester, DEHP, appeared in the mid 1940-1950s, and decreased towards the surface. Trace elements fell roughly into three groups. Fe, Mn, and As were in approximately constant proportion to Al, except in some deeper, sandy sediments, where they showed enrichments linked to redox conditions. Ag, Cd, Cu, Hg, Pb, and Zn had low concentrations in the deepest sediments, high concentrations at mid-depths, and declines to intermediate levels at the surface. Ni and Cr followed neither of these patterns closely. We observed that many contaminants appeared in the Anacostia sediments at various times, and reached relatively high concentrations in the past, but are now showing declines in loadings. In some cases, such as PCBs, DDT, chlordane, and Pb from leaded gasoline, these declines can be clearly linked to the discontinuation of their use for environmental reasons. For other contaminants (e.g., PAHs, DEHP, selected metals) these declines are more likely the result of changes in production, usage and waste control.     

Augmenting Groundwater Monitoring Networks near Landfills with Slurry Cutoff Walls

This study investigated the use of slurry cutoff walls in conjunction with monitoring wells to detect contaminant releases from a solid waste landfill. The 50 m wide by 75 m long landfill was oriented oblique to regional groundwater flow in a shallow sand aquifer. Computer models calculated flow fields and the detection capability of six monitoring networks, four including a 1 m wide by 50 m long cutoff wall at various positions along the landfill's downgradient boundaries and upgradient of the landfill. Wells were positioned to take advantage of convergent flow induced downgradient of the cutoff walls. A five-well network with no cutoff wall detected 81% of contaminant plumes originating within the landfill's footprint before they reached a buffer zone boundary located 50 m from the landfill's downgradient corner. By comparison, detection efficiencies of networks augmented with cutoff walls ranged from 81 to 100%. The most efficient network detected 100% of contaminant releases with four wells, with a centrally located, downgradient cutoff wall. In general, cutoff walls increased detection efficiency by delaying transport of contaminant plumes to the buffer zone boundary, thereby allowing them to increase in size, and by inducing convergent flow at downgradient areas, thereby funneling contaminant plumes toward monitoring wells. However, increases in detection efficiency were too small to offset construction costs for cutoff walls. A 100% detection efficiency was also attained by an eight-well network with no cutoff wall, at approximately one-third the cost of the most efficient wall-augmented network.     

RISK ASSESSMENT METHODOLOGY FOR KARST AQUIFERS: (2) SOLUTE-TRANSPORT MODELING

Ground-water flow and solute-transport simulation modeling are major components of most exposure and risk assessments of contaminated aquifers. Model simulations provide information on the spatial and temporal distributions of contaminants in subsurface media but are difficult to apply to karst aquifers in which conduit flow is important. Ground-water flow and solute transport in karst conduits typically display rapid-flow velocities, turbulent-flow regimes, concentrated pollutant-mass discharge, and exhibit open-channel or closed-conduit flow. Conventional ground-water models, dependent on the applicability of Darcy`s law, are inappropriate when applied to karst aquifers because of the (1) nonapplicability of Darcian-flow parameters, (2) typically nonlaminar flow regime, and (3) inability to locate the karst conduits through which most flow and contaminant transport occurs. Surface-water flow and solute-transport models conditioned on a set of parameters determined empirically from quantitative ground-water tracing studies may be effectively used to render fate-and-transport values of contaminants in karst conduits. Hydraulic-flow and geometric parameters developed in a companion paper were used in the surface-water model, TOXI5, to simulate hypothetical slug and continuous-source releases of ethylbenzene in a karst conduit. TOXI5 simulation results showed considerable improvement for predicted ethylbenzene-transport rates and concentrations over qualitative tracing and analytical ground-water model results. Ethylbenzene concentrations predicted by TOXI5 simulations were evaluated in exposure and risk assessment models.     

Colloid-Associated Groundwater Contaminant Transport in Homogeneous Saturated Porous Media: Mathematical and Numerical Modeling

During the past two decades, significant efforts have been made to study contaminant transport in the presence of colloids. Several researchers reported that colloidal particles could enhance the migration of contaminants in groundwater by reducing retardation factor. When the colloidal particles are present in the aquifer, the subsurface system can be considered as a three-phase system with two solid phases and an aqueous phase. The interaction between contaminants, colloids, and solid matrix should be considered in assessing the fate and transport of the contaminant in the groundwater flow system. In this study, a one-dimensional numerical model is developed by employing a fully implicit finite difference method. This model is based on mass balance equations and mass partition mechanisms between the carriers and solid matrix, as well as between the carriers and contaminants in a saturated homogeneous porous medium. This phenomenon is presented by two approaches: equilibrium approach and fully kinetic first-order approach. The formulation of the model can be simplified by employing equilibrium partitioning of particles. However, contaminant transport can be predicted more accurately in realistic situations by kinetic modeling. To test the sensitivity of the model, the effect of the various chemical and physical coefficients on the migration of contaminant was investigated. The results of numerical modeling matched favorably with experimental data reported in the literature.     

Water pinch analysis for water and wastewater minimization in Tehran oil refinery considering three contaminants

This study aims to find an appropriate way to minimize water utility in the petrochemical and petroleum industries due to high rate of water consumption. For this purpose, Tehran oil refinery has been well studied. In this research, three key contaminants including suspended solid, hardness as well as COD have been considered to analyze the water network. In addition, the potential of water reuse was studied for all methods. These key contaminants once were analyzed separately as a single contaminant and the amount of required freshwater was calculated for them. In this stage, amount of freshwater was reduced to about 60.9 (17%), 203 (59.7%) and 143 m³/h (42.5%) in terms of suspended solids, hardness, and COD, respectively. Water minimization within operations for suspended solids is less than two others. Therefore, this is a limiting contaminant and can be selected as a key contaminant. In the next stage, three contaminants were analyzed two by two based on their mass transfer. Results show that, in the targeting for minimization based on the suspended solids and hardness, the amount of required water is reduced to 142.74 m³/h or 42%. This amount for suspended solids and COD is equal to 86.3 m³/h (26%) and for COD and hardness is 124 m³/h (37%). Analyzing the methods shows that the method based on the double contaminant gives more precise results rather than single contaminant.     

Assessment of coastal storm impacts on contaminant body burdens of oysters collected from the gulf of Mexico

This study evaluated changes in oyster tissue contaminant levels following North Atlantic tropical cyclones to determine if changes in contaminant concentrations were predictable. The basis for this study was analysis of coastal chemical contaminant data from the National Oceanic and Atmospheric Administration's (NOAA) National Status and Trends Mussel Watch Program and NOAA's National Weather Service storm track data. The tendency for contaminant (metals and organic compounds) body burdens to increase or decrease in oyster tissue after a storm was assessed using contingency and correspondence analyses. Post-storm contaminant levels in oysters revealed a consistent pattern of distribution, which could be described as follows: (1) most of the organic contaminants stay within their long-term concentration ranges, (2) very few organic contaminants decreased, and (3) metals overwhelmingly tend to increase.     

Statistical trends in ground-water monitoring data at a landfill Superfund site: A case study

This paper describes the use of statistical regression models to characterize temporal trends in groundwater monitoring data collected between 1980 and 1990 on 15 wells and 13 parameters (195 cases in all) at the KL Avenue landfill site in Kalamazoo County, Michigan. This site was used as a municipal landfill prior to 1980, then was placed on the Superfund site list in 1982 after ground-water contamination was found.Six temporal regression trend models were defined using linear and quadratic regression models. These trends were used to classify each of the 195 cases as: improving, deteriorating, or stable over the 1980–1990 time period. Using these classifications it was determined that there were more than twice as many improving cases as deteriorating conditions at the KL site during this time period. These models provide a method for visualizing and interpreting trends in ground-water quality at individual well locations within the contaminant plume and for assessing the chemical trend behavior of the overall plume. The improving, deteriorating, and stable trend categories were developed for two purposes. The first purpose is to facilitate comprehension of information contained in large amounts of water quality data. The second is to assist communication among the many different groups of people who recommend actions, including remediation responsibilities at Superfund sites, like the KL site.A normal probability model was used in the trend classifications. This model contained provisions to accommodate nondetect data and other abnormal laboratory determinations which can influence the trend selection process. The robustness of this classification procedure was examined using a lognormal probability model. The overall conclusions about the KL site using the lognormal model were similar to those obtained using the normal model. However, some individual trend indications were different using the lognormal model. The Shapiro-Wilk test was used to check the adequacy of both the normal and lognormal models. The lognormal model was found to be a somewhat more adequate model for fitting the KL site data, but was not found to be superior to the normal model for each case.The normal and lognormal models were both found to be suitable for determining overall trend conditions at this site. Both models are recommended for these purposes assuming an understanding of the statistical constraints and hydrochemical context. However, it is recommended that the search for more adequate trend models continues.