The removal kinetics of dissolved organic matter and the optical clarity of groundwater
Concentrations of dissolved organic matter (DOM) and ultraviolet/visible light absorbance decrease systematically as groundwater moves through the unsaturated zones overlying aquifers and along flowpaths within aquifers. These changes occur over distances of tens of meters (m) implying rapid removal kinetics of the chromophoric DOM that imparts color to groundwater. A one-compartment input-output model was used to derive a differential equation describing the removal of DOM from the dissolved phase due to the combined effects of biodegradation and sorption. The general solution to the equation was parameterized using a 2-year record of dissolved organic carbon (DOC) concentration changes in groundwater at a long-term observation well. Estimated rates of DOC loss were rapid and ranged from 0.093 to 0.21 micromoles per liter per day (μM d−1), and rate constants for DOC removal ranged from 0.0021 to 0.011 per day (d−1). Applying these removal rate constants to an advective-dispersion model illustrates substantial depletion of DOC over flow-path distances of 200 m or less and in timeframes of 2 years or less. These results explain the low to moderate DOC concentrations (20–75 μM; 0.26–1 mg L−1) and ultraviolet absorption coefficient values (a254 < 5 m−1) observed in groundwater produced from 59 wells tapping eight different aquifer systems of the United States. The nearly uniform optical clarity of groundwater, therefore, results from similarly rapid DOM-removal kinetics exhibited by geologically and hydrologically dissimilar aquifers.
KeywordsHydrochemistry Dissolved organic carbon Reaction kinetics USA
Cinétiques d’élimination de la matière organique dissoute et clarté optique des eaux souterraines
Les concentrations de la matière organique dissoute (MOD) et l’absorption dans l’ultraviolet décroissent systématiquement quand l’eau souterraine se déplace à travers les zones non saturées au-dessus et à l’intérieur des aquifères et dans la zone saturée des aquifères. Ces variations se produisent sur quelques dizaines de mètres de distance ce qui implique des cinétiques d’élimination rapide des MOD chromophores qui donnent sa couleur à l’eau souterraine. Un modèle à un compartiment d’entrée-sortie a été utilisé pour dériver l’équation différentielle représentant l’élimination de la MOD de la phase dissoute due aux effets combinés de la biodégradation et de la sorption. La solution générale de l’équation a été paramétrée en utilisant l’enregistrement sur deux ans des variations à long terme de la concentration dans l’eau souterraine du carbone organique dissous (COD) sur un piézomètre. Les taux estimés de perte de MOD sont rapides, compris entre 0.093 et 0.210 micromoles par litre et par jour (μM d−1), et les constantes de taux d’élimination de la MOD sont comprises entre 0.0021 et 0.011 par jour (j−1). L’application de ces constantes de taux d’élimination à un modèle d’advection-dispersion illustre de substantielles diminutions de la MOD chromophore sur des distances d’écoulement de 200 m ou moins et dans des laps de temps de deux ans ou moins. Ces résultats expliquent les concentrations faibles à modérées en COD (20–75 μM ; 0.26–1 mg L−1) et les valeurs du coefficient d’absorption dans l’ultraviolet (a254 < 5 m−1) observées dans les eaux souterraines plus âgées prélevées dans 59 puits exploitant 8 systèmes aquifères différents des Etats-Unis d’Amérique. La clarté optique quasi uniforme des eaux souterraines résulte, par conséquent, des cinétiques identiquement rapides de l’élimination de la MOD présentées par des aquifères différents du point de vue géologique et hydrogéologique.
La cinética de eliminación de la materia orgánica disuelta y la transparencia óptica del agua subterránea
Las concentraciones de la materia orgánica disuelta (DOM) y la absorción ultravioleta disminuyen sistemáticamente cuando el agua subterránea se mueve a través de las zona no saturada suprayacente y dentro de los acuíferos y en las zonas saturadas de los acuíferos. Estos cambios ocurren a distancias de decenas de metros (m) lo cual implica una rápida cinética de eliminación de cromóforos de la DOM que le imparten color al agua subterránea. Se utilizó un modelo de entrada-salida de un compartimiento para derivar una ecuación diferencial que describe la eliminación de la fase disuelta de DOM debido a los efectos combinados de la biodegradación y de la sorción. Se parametrizó la solución general de la ecuación utilizando un registro de dos años de cambios en la concentración de carbono orgánico disuelto (DOC) en el agua subterránea a largo plazo en un pozo de observación. Las tasas de pérdidas estimadas de DOC fueron rápidas y variaron entre 0.093 y 0.21 micromoles por litro por día (μM d−1), y la constante de la velocidad de eliminación del DOC osciló entre 0.0021 y 0.011 por día (d−1). La aplicación de estas constantes de velocidad de eliminación a un modelo de advección-dispersión ilustra el agotamiento sustancial del cromóforo de la DOM a través de distancias de trayectoria de flujo de 200 m o menos, y en un plazo de dos años o menos. Estos resultados explican la baja a moderada concentración de DOC (20–75 μM; 0.26–1 mg L−1) y los valores de coeficientes de absorción ultravioleta (a254 < 5 m−1) observados en el agua subterránea más antigua generada a partir de 59 pozos en ocho sistemas de acuíferos diferentes de Estados Unidos. La transparencia óptica casi uniforme del agua subterránea, por lo tanto, resulta de la manera similar de una rápida cinética de eliminación de DOM exhibida por acuíferos geológica e hidrológicamente disímiles.
地下水在上覆非饱和带以及含水层饱和带流动时,溶解有机物含量(DOM)和紫外吸收率降低。在几十米的距离内就会出现此种情况,意味着载色体溶解有机物快速除去动力学作用,载色体溶解有机物会染色地下水。利用一个隔间的投入产出模型导出描述从溶解相中除去溶解有机物的方程式,生物降解吸附作用的综合影响造成了有机物的溶解相。方程式是利用长期观测井中地下水溶解有机物含量变化的两年记录进行参数化一般解。估算的溶解有机物损失率估计的快速和范围从0.093到0.21微摩尔每升每一天(μM d−1)。去除速率常数为0.0021 ~ 0.011每天(d−1)。在对流扩散模型中应用这些除去率常数描述了DOM在2年或更少的时间在200米以内的水流通道上的实际损耗量。从美国八个不同含水层系统59个井中获取的地下水中溶解有机物低到中等的含量(20–75 μM; 0.26–1 mg L−1)及紫外吸附系数值(a254 < 5 m−1),地下水光学透明性几乎相同,是由地质上和水文上不同含水层所展示的类似于溶解有机物快速去除动力学的表现结果。
A cinética da remoção da matéria orgânica dissolvida e a transparência ótica da água subterrânea
As concentrações da matéria orgânica dissolvida (MOD) e a absorbância ultravioleta decrescem sistematicamente à medida que a água subterrânea se move através das zonas não saturadas sobrepostas e no seio de aquíferos e no interior das zonas saturadas dos aquíferos. Estas mudanças ocorrem em distâncias da ordem das dezenas de metros (m) significando rápidas cinéticas de remoção da MOD cromofórica que é responsável por dar cor à água subterrânea. Foi usado um modelo de compartimento único com entrada-saída para desenvolver equações diferenciais que descrevem a remoção da MOD a partir da fase dissolvida devido aos efeitos combinados da biodegradação e da sorção. A solução geral da equação foi parametrizada utilizando um registro de dois anos de mudanças de concentração de carbono orgânico dissolvido (COD) num poço com observações estendidas no tempo. As taxas calculadas para a perda de COD foram rápidas e variaram desde 0.093 a 0.21 micromoles por litro por dia (μM d−1) e as constantes de velocidade para a remoção do COD variaram entre 0.0021 e 0.011 por dia (d−1). A aplicação destas constantes de velocidade de remoção num modelo de adveção-dispersão mostra uma perda substancial de MOD cromofórica ao longo de percursos de fluxo de 200 m ou menos e em períodos de tempo de dois anos ou menos. Estes resultados explicam as concentrações baixas ou moderadas de COD (20–75 μM; 0.26–1 mg L−1) e os coeficientes de absorção de ultravioleta (a254 < 5 m−1) observados em águas subterrâneas mais antigas produzidas por 59 poços que intersetam oito sistemas aquíferos diferentes nos Estados Unidos. A quase uniforme transparência ótica da água subterrânea resulta, em consequência, de cinéticas de remoção da MOD semelhantemente rápidas que são exibidas por aquíferos geológica e hidrologicamente distintos.
Among the most remarkable and valued properties of groundwater, and the spring waters derived from groundwater systems, is their striking optical clarity (Davies-Colley and Smith 1995). This clarity, and thus the perceived healthfulness of groundwater relative to many surface waters, has had a profound effect on the history of human water use. Many of the mythologies that have traditionally surrounded groundwater (Bord and Bord 1985) can be traced directly to its clarity relative to most surface waters. More recently, the bottled water industry in the United States was founded in the 19th century on the perception that optically clear spring waters were healthier than municipal water supplies derived from surface-water sources (Chapelle 2005). Finally, the earliest scientific studies of groundwater geochemistry can be traced directly to curiosity about the chemical and optical purity of spring waters (Back et al. 1995). Surprisingly, however, the fundamental hydrologic and geochemical processes that lead to the nearly uniform optical clarity of groundwater are not widely understood.
Although groundwater that has visible color does occur (Tan and Sudak 1992; McConnell and Hacke 1993) it is relatively rare. Much of the color associated with natural groundwater and surface water is due to the presence of dissolved organic matter (DOM), some fraction of which absorbs ultraviolet (UV) and visible (V) light thereby conferring color. This color-producing DOM is referred to as chromophoric dissolved organic matter or CDOM (Blough and Del Vecchio 2002; Fichot and Benner 2011). The lack of color in groundwater compared to many surface waters is largely due to the relative absence of CDOM. However, if one considers that CDOM-laden surface waters are the principal sources of recharge to most groundwater systems (DeSimone et al. 2014), it is not intuitively obvious that groundwater should exhibit such near-universal lack of color.
For example, surface water from the black-water Withlacoochee River in southern Georgia, with a median total organic carbon (TOC) concentration of 1,200 micromoles per liter (μM); 16 milligrams per liter (mg L−1) and median color of 110 potassium-cobalt units (PCU), drains directly into the karstic Floridan aquifer via sinkholes in the river channel (McConnell and Hacke 1993). Within 200 meters (m) of the recharge zone, TOC concentrations in groundwater decline to less than 300 μM (3.9 mg L−1) and the color decreases proportionally. By the time the “plume” of river-derived water has been transported 10 km downgradient, the color disappears completely (<1 PCU). This shows that the Floridan aquifer has a substantial capacity to attenuate CDOM concentrations, a characteristic that could explain the striking clarity (PCU ~ 0) of many spring waters derived from the Floridan aquifer such as Silver Springs (Schmidt 2001). In addition, this raises the possibility that other groundwater systems have similar CDOM-attenuating properties.
The dynamics of DOM moving through soils are important in regulating the transport of carbon, and thus energy, within terrestrial ecosystems and have been the subject of extensive study (Neff and Asner 2001). These studies have shown that biodegradation and sorption combine to remove DOM from groundwater circulating though soils and aquifer sediments (Neff and Asner 2001; Kalbitz et al. 2003; Findlay and Sobczak 1996; Baker et al. 2000; Shen et al. 2015). The water-purifying properties of sandy soils have been known for centuries, and were the underlying technology for the famous filter-cisterns in use in Venice, Italy since the first millennia BCE (Chapelle 2005). More recently, engineered artificial recharge systems have been used to remove DOM from recycled treated wastewaters (Rauch and Drewes 2005; Grünheid et al. 2005). Curiously, however, the more universal issue of DOM- and CDOM-removal processes from the soil and surface waters that naturally recharge regional aquifer systems, and their impact on the optical clarity of groundwater, has received less attention.
The purpose of this paper is to develop a method to quantify the removal kinetics of DOM in groundwater using data from a long-term monitoring well. These DOM removal kinetics are then used to provide a quantitative explanation for the uniform clarity of groundwater produced from 59 observation wells tapping eight hydrologically diverse aquifer systems of the United States.
Materials and methods
The SC Piedmont (Shen et al. 2015), SC Coastal plain (Chapelle et al. 2011), Floridan, Illinois, and Connecticut aquifer systems are characterized by humid climatic conditions and relatively rapid recharge rates. The California Central Valley, High Plains, Salt Lake, and Colorado Platueau aquifers are characterized by more arid conditions and lower recharge rates. The Floridan and Edwards-Trinity aquifers are karstic carbonate-rock aquifers, the SC Piedmont is a fractured metamorphic rock aquifer, whereas the others are clastic aquifers of sedimentary origin. The Connecticut and Illinois aquifer systems are predominantly of glacial origin, and the Central Valley, High Plains, the SC Coastal Plain, Colorado Plateau, and Salt Lake aquifers are largely fluvial in origin. The aquifer systems included in this study, therefore, represent a wide variety of geologic and hydrologic conditions.
A single long-term USGS monitoring well in the SC Piedmont (Shen et al. 2015) was used to study variations in DOC concentrations and UV absorbance in groundwater over time. The location of the SC Piedmont site is shown in Fig. 1. This well is part of the South Carolina Climate Response Network (Station 340837081173800; Name RIC- 748) and is located in a forested area of Richland County (Fig. 1). Groundwater samples for DOC analysis were collected at approximately monthly intervals (n = 24) between 2010 and 2012 as previously described (Shen et al. 2015). In addition, concentrations of dissolved oxygen (DO) were measured for each sampling event in the field using the Rhodazine D™ method for low-range (<1 mg L−1) concentrations of DO (CHEMetrics Inc 2016). Field measurements for temperature, specific conductivity, and pH were made for each sampling event with a YSI model 556 multi-parameter water-quality sonde (YSI Inc 2016). Concentrations of dissolved iron (Hach 2015a) and sulfide (Hach 2015b) were measured periodically.
Where Aλ is the absorbance measured across pathlength r at a wavelength λ (254 nm). The time-series DOC concentrations at the USGS observation well have been previously published by Shen et al. (2015).
Regression analyses were used to compute a DOC/a254 evolution pathway for SC Piedmont and Coastal Plain samples, and to estimate kinetic parameters for DOC removal. These regressions were computed using SigmaPlot 11.02 (SigmaPlot 2009). Solutions to the advective-dispersion equation used to illustrate the effects of DOC removal kinetics on DOC concentrations in groundwater were obtained using the method of Domenico (1987). The EPA Bioscreen software package (EPA 2016), which incorporates the analytic solution provided by Domenico (1987), was used to solve the advective-dispersion equation. Values for the longitudinal hydrodynamic dispersion tensor used in the advective-dispersion equation were estimated from a dispersivity (0.66 m) appropriate for the horizontal scale of the solution domain (200 m; Gelhar et al. 1992) and the simulated groundwater velocities.
DOC concentrations and UV absorbance in groundwater
The observed patterns of DOC concentrations and a254 shown in Figs. 2 and 3, which occur over distances of tens of meters, imply that the kinetics of DOC removal are relatively rapid. However, lacking precise knowledge of soil water and groundwater seepage rates, and initial and final DOC concentrations (Findlay and Sobczak 1996; Baker et al. 2000; Rauch and Drewes 2005; Grünheid and et al. 2005), the kinetics of DOC removal cannot be quantified using the data of Figs. 2 and 3.
DOC concentration changes over time
The changes in DOC concentrations and a254 in groundwater of the SC Piedmont and Coastal Plain aquifers (Figs. 2 and 3) represent samples collected at one discrete point in time. In order to investigate variations in DOC concentrations over time, samples of groundwater from a USGS long-term monitoring well in the SC Piedmont aquifer were collected monthly for 2 years as described previously by Shen et al. (2015). During the 2-year period, concentrations of dissolved oxygen (DO) ranged from 0.6 to 1.2 mg L−1, temperature ranged from 15 to 16 ° C, specific conductivity ranged from 899 to 976 μSi/cm, and concentrations of dissolved iron (0.03 mg L−1) and dissolved sulfide (<0.01) were consistently low. These data indicate that oxic conditions characterized by relatively low DO concentrations were predominant in groundwater tapped by the monitoring well.
Where x(t) are DOC concentrations as a function of time in micromoles per liter (μM), C1 and C2 are constants of integration (μM), and k is the first-order removal rate constant (T−1). When t=0, x = C1 + C2, which is the initial concentration of DOC in the aquifer following a recharge event. As t becomes large following the recharge event, the second term of Eq. (2) approaches zero and x(t) → C1. C1, therefore, represents DOC that is recalcitrant to biodegradation and sorption and thus remains in solution after the reactive DOC fraction (C2) has been removed (Grünheid et al. 2005).
The estimates of DOC loss range from 0.093 to 0.21 micromoles per liter per day (μM d−1) and the DOC removal rate constants for time periods A, B, and C range from 0.0021 to 0.011 d−1 (Fig. 6). Biodegradation experiments conducted with groundwater produced from the observation well by Shen et al. (2015) estimated a biodegradation rate constant of 0.0032 d−1, suggesting that biodegradation is the predominant process causing the observed DOC concentration declines over time. Regardless of the relative contribution of the different removal processes, these estimates indicate that the removal rate of DOC is relatively rapid, ranging from about 1.1 to 0.21 % d−1. The range of DOC removal rates and the rate constants associated with DOC removal estimated in this study are broadly consistent with rates observed in other groundwater systems (Findlay and Sobczak 1996; Baker et al. 2000; Rauch and Drewes 2005; Grünheid et al. 2005). This, in turn, suggests that the kinetics of DOC removal are similarly rapid in a variety of groundwater systems.
These simulations indicate substantial removal of DOC from groundwater in less than 200 m of flowpath and in less than 2 years of transport time. A groundwater seepage velocity of 100 m/ yr−1 is relatively high (Gelhar et al. 1992), but is representative of karstic carbonate aquifers such as the Floridan aquifer in southern Georgia (McConnell and Hacke 1993); thus, the 100 m yr−1 simulation illustrates the higher end of both transport time and distance. As seepage velocity decreases, the distance and time of DOC transport decreases proportionally (Fig. 7b). The simulations of Fig. 7 show DOC concentrations approaching zero over time, which is equivalent to setting C1 in Eq. (3) equal to zero. In reality, it is observed that C1 is greater than zero in groundwater systems (Fig. 6), representing relatively non-reactive DOC, and DOC concentrations approach that value (C1) during transport (Grünheid et al. 2005).
The simulations shown in Fig. 7 are broadly consistent with empirical studies in a variety of groundwater systems which have reported substantial DOC removal over flowpath lengths of tens to hundreds of meters (Findlay and Sobczak 1996; Baker et al. 2000; Rauch and Drewes 2005; Grünheid et al. 2005). Finally, these simulations are consistent with the observed rapid loss of both DOC and color along the flowpath of the Floridan aquifer in response to recharge from the black-water Withlacoochee River in southern Georgia (McConnell and Hacke 1993).
Similarity of DOC concentrations and UV absorbance in different groundwater systems
A closer look at the DOC concentrations between zero and 100 μM and the corresponding a254 values (Fig. 8b) reveals variability in the data that is not apparent at the scale of Fig. 8a. First, the majority of the DOC/a254 values fall below the SC Piedmont and Coastal Plain curve, although the slope of the curve is similar to the slope of the observed data. Secondly, several of the samples from the Edwards-Trinity aquifer and California Central Valley aquifer plot above the SC Piedmont and Coastal Plain curve. Those samples were characterized by relatively high nitrate concentrations (~500 μM). Because dissolved nitrate is a UV chromophore (Collos et al. 1999), this may contribute to the elevated a254 values relative to the lower-nitrate (<80 μM) groundwater produced from the other aquifers. This also illustrates that CDOM is not the only chromophore that can be found in groundwater. The rest of the observed variability may reflect (1) differences in DOM quality in the water recharging these different aquifers, (2) differences in aquifer material that exhibits different sorption behavior to DOM and (3) differences in redox conditions and available terminal electron acceptors that influence the bioavailability of DOM.
Groundwater ages for the aquifer systems sampled for this study have been evaluated with a variety of techniques including tritium, chlorofluorocarbons, and carbon-14 (DeSimone et al. 2014; Katz 2004; McMahon et al. 2004). Mean groundwater ages (time since recharge) for the eight aquifer systems range from a low of 10 years (Connecticut) to greater than 15,000 years (Colorado Plateau). Given the rapid rate of DOC removal suggested by the simulations of Fig. 7, groundwater from each of the eight aquifer systems will have undergone substantial DOM removal prior to the time of sampling. This, in turn, provides an explanation for the clustering of median DOC concentrations (17.6 μM; 0.22 mg L−1) and median a254 values (0.92 m−1) for the samples shown in Fig. 8.
These results are broadly consistent with those of Leenheer et al. (1974) in a survey of DOC concentrations measured in groundwater produced from 100 wells located throughout the United States which reported a median DOC concentration of 54 μM (0.7 mg L−1). This suggests that background concentrations of relatively non-reactive DOC in groundwater (C1 in Eq. 3) are typically on the order of 20–75 μM (0.26–1 mg L−1). Interestingly, the range of C1 values indicated by Fig. 8 is similar to the C1 estimates observed from the long-term monitoring well data (Fig. 6). Finally, and also consistent with the current results (Fig. 8), Leenheer et al. (1974) reported that DOC concentrations did not vary significantly between aquifers of different lithologies.
The results of this study provide an explanation for the nearly uniform optical clarity that characterizes groundwater in a variety of geologic media and under different hydrologic conditions. Whereas waters originating at land surface and recharging groundwater systems often contain high concentrations of CDOM, this CDOM is rapidly attenuated in the unsaturated zone overlying aquifers and in the saturated zone of the aquifers. Virtually any groundwater that has been recharged from land surface, and which has circulated in the subsurface for more than a few years, will have had much of its CDOM removed. This is why the springs tapping the Floridan aquifer, which are recharged by high CDOM surface waters, produce brilliantly clear water (Schmidt 2001) despite being relatively young (~20 years since recharge; Katz 2004). The striking clarity of these and other ground- and spring-waters, therefore, is a direct result of the rapid removal kinetics of DOM in groundwater systems.
This research was funded by the National Water Quality Assessment (NAWQA) and Toxic Substances Hydrology programs of the US Geological Survey. The authors would like to thank Robert C. Sharpley of the Interdisciplinary Mathematics Institute, University of South Carolina, for reviewing an early version of this manuscript. Use of trade, firm, or product names is for descriptive purposes only and does not imply endorsement by the US Government.
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