groundwater quality; trend detection; trend extrapolation; modelling; nitrate; heavy metals
Abstract :
[en] Land use changes and the intensification of agriculture since the 1950s have resulted in a deterioration of groundwater quality in many European countries. For the protection of groundwater quality, it is necessary to (1) assess the current groundwater quality status, (2) detect changes or trends in groundwater quality, (3) assess the threat of deterioration and (4) predict future changes in groundwater quality. A variety of approaches and tools can be used to detect and extrapolate trends in groundwater quality, ranging from simple linear statistics to distributed 3D groundwater contaminant transport models. In this paper we report on a comparison of four methods for the detection and extrapolation of trends in groundwater quality: (1) statistical methods, (2) groundwater dating, (3) transfer functions, and (4) deterministic modeling. Our work shows that the selection of the method should firstly be made on the basis of the specific goals of the study (only trend detection or also extrapolation), the system under study, and the available resources. For trend detection in groundwater quality in relation to diffuse agricultural contamination, a very important aspect is whether the nature of the monitoring network and groundwater body allows the collection of samples with a distinct age or produces samples with a mixture of young and old groundwater.
We conclude that there is no single optimal method to detect trends in groundwater quality across
widely differing catchments.
R. F. Spalding M. E. Exner Occurrence of nitrate in groundwater - a review J. Environ. Qual. 1993 22 3 392 402
S. S. D. Foster A. C. Cripps A. Smith-Carington Nitrate leaching to groundwater Philos. Trans. R. Soc. London, Ser. B 1982 296 477 489
O. Strebel W. H. M. Duynisveld J. Böttcher Nitrate pollution of groundwater in western Europe Agric., Ecosyst. Environ. 1989 26 3-4 189 214
B. T. Nolan et al. Risk of nitrate in groundwaters of the United States - a national perspective Environ. Sci. Technol. 1997 31 8 2229
EU, Directive of the European Parliament and of the Council 2000/60/EC Establishing a Framework for Community Action in the Field of Water Policy, 2000
EU, Directive 2006/118/EC on the Protection of Groundwater against Pollution and Deterioration, 2006
J. Y. Lee et al. A review of the national groundwater monitoring network in Korea Hydrol. Process. 2007 21 7 907 919
N. J. Kim M. J. Cho N. C. Woo Developing a national groundwater- monitoring network in Korea Hydrogeol. J. 1995 3 4 89
R. K. Juhler G. Felding Monitoring methyl tertiary butyl ether (MTBE) and other organic micropollutants in groundwater: results from the Danish national monitoring program Water, Air, Soil Pollut. 2003 149 1-4 145
W. Van Duijvenbooden, Groundwater Quality Monitoring in the Netherlands, in Regional Groundwater Quality, ed., W. M. Alley, Van Nostrand Reinhold, New York, 1993, pp. 515-535
C. J. Daughney R. R. Reeves Definition of hydrochemical facies in the New Zealand national groundwater monitoring programme J. Hydrol. (New Zealand) 2005 44 2 105 130
M. N. Almasri S. M. S. Ghabayen Analysis of nitrate contamination of Gaza Coastal Aquifer, Palestine Journal of Hydrologic Engineering 2008 13 3 132 140
P. P. Leahy B. Ryan I. Johnson An introduction to the U.S. geological surveys national water-quality assessment program Water Resources Bulletin 1993 29 4 529
M. R. Rosen W. W. Lapham Introduction to the U.S. Geological Survey National Water-Quality Assessment (NAWQA) of ground-water quality trends and comparison to other national programs J. Environ. Qual. 2008 37 S5 190 198
R. S. Ward et al. A framework for monitoring regional groundwater quality Q. J. Eng. Geol. Hydrogeol. 2004 37 4 271 281
C. J. Daughney R. R. Reeves Analysis of temporal trends in New Zealand's groundwater quality based on data from the national groundwater monitoring programme J. Hydrol. (New Zealand) 2006 45 1 41 62
Y. Xu L. A. Baker P. C. Johnson Trends in ground water nitrate contamination in the Phoenix, Arizona Region Ground Water Monit. Rem. 2007 27 2 49 56
M. E. Stuart et al. Screening for long-term trends in groundwater nitrate monitoring data Q. J. Eng. Geol. Hydrogeol. 2007 40 4 361 376
H. P. Broers and et al., Groundwater quality trend detection at the regional scale: effects of spatial and temporal variability, IAHS Publ., 2005, vol. 297, pp. 50-60
H. P. Broers B. Van der Grift Regional monitoring of temporal changes in groundwater quality J. Hydrol. (Amsterdam, Neth.) 2004 296 1-4 192 220
J. Reynolds-Vargas J. Fraile-Merino R. Hirata Trends in nitrate concentrations and determination of its origin using stable isotopes ( 18O and 15N) in groundwater of the western Central Valley, Costa Rica Ambio 2006 35 5 229 236
J. Batlle-Aguilar et al. Identification of groundwater quality trends in a chalk aquifer threatened by intensive agriculture in Belgium Hydrogeol. J. 2007 15 8 1615
K. Burow N. Dubrovsky J. Shelton Temporal trends in concentrations of DBCP and nitrate in groundwater in the eastern San Joaquin Valley, California, USA Hydrogeol. J. 2007 15 5 991 1007
J. C. Loftis Trends in groundwater quality Hydrol. Process. 1996 10 335 355
Regional Ground-Water Quality, ed., W. M. Alley, Van Nostrand Reinhold, New York, 1993
J. K. Böhlke J. M. Denver Combined use of groundwater dating, chemical, and isotopic analyses to resolve the history and fate of nitrate contamination in two agricultural watersheds, Atlantic coastal plain, Maryland Water Resour. Res. 1995 31 9 2319 2339
A. M. MacDonald et al. Identifying trends in groundwater quality using residence time indicators: an example from the Permian aquifer of Dumfries, Scotland Hydrogeol. J. 2003 11 4 504 517
J. K. Böhlke et al. Denitrification in the recharge area and discharge area of a transient agricultural nitrate plume in a glacial outwash sand aquifer, Minnesota Water Resour. Res. 2002 38 7 1 26
L. I. Wassenaar M. J. Hendry N. Harrington Decadal geochemical and isotopic trends for nitrate in a transboundary aquifer and implications for agricultural beneficial management practices Environ. Sci. Technol. 2006 40 15 4626 4632
A. J. Tesoriero et al. Nitrogen transport and transformations in a coastal plain watershed: influence of geomorphology on flow paths and residence times Water Resour. Res. 2005 41 2 W02008
T. Laier, Nitrate Monitoring and CFC-Age Dating of Shallow Groundwaters - An Attempt to Check the Effect of Restricted Use of Fertilizers, in Nitrate in Groundwaters, IAH Selected Papers on Hydrogeology, ed., L. Razowska-Jaworek, and, A. Sadurski, A.A. Balkema, Leiden, The Netherlands, 2004, pp. 247-258
A. Visser et al. Demonstrating trend reversal of groundwater quality in relation to time of recharge determined by 3H/3He Environ. Pollut. 2007 148 3 797 807
K. K. Gardner R. M. Vogel Predicting ground water nitrate concentration from land use Ground Water 2005 43 3 343 352
Y. Jiang et al. Groundwater quality and land use change in a typical karst agricultural region: a case study of Xiaojiang watershed, Yunnan Journal of Geographical Sciences 2006 16 4 405 414
A. Ritter et al. Agricultural land use and hydrology affect variability of shallow groundwater nitrate concentration in South Florida Hydrol. Process. 2007 21 18 2464 2473
D. J. Lapworth et al. Pesticides in groundwater: some observations on temporal and spatial trends Water and Environment Journal 2006 20 2 55 64
H. J. Di et al. A pilot regional scale model of land use impacts on groundwater quality Management of Environmental Quality 2005 16 3 220 234
M. N. Almasri J. J. Kaluarachchi Modular neural networks to predict the nitrate distribution in ground water using the on-ground nitrogen loading and recharge data Environmental Modelling and Software 2005 20 7 851 871
M. N. Almasri J. J. Kaluarachchi Modeling nitrate contamination of groundwater in agricultural watersheds J. Hydrol. (Amsterdam, Neth.) 2007 343 3-4 211
J. C. Refsgaard et al. Large scale modelling of groundwater contamination from nitrate leaching J. Hydrol (Amsterdam, Neth.) 1999 221 3-4 117 140
B. Van der Grift J. Griffioen Modelling assessment of regional groundwater contamination due to historic smelter emissions of heavy metals J. Contam. Hydrol. 2008 96 1-4 48 68
J. Grath, et al., The EU Water Framework Directive: Statistical aspects of the identification of groundwater pollution trends, and aggregation of monitoring results. Final Report, 41.046/01-IV1/00 and GZ 16 2500/2-I/6/00, Austrian Federal Ministry of Agriculture and Forestry, Environment and Water Management and European Commission, Vienna, 2001
P. Quevauviller Groundwater monitoring in the context of EU legislation: reality and integration needs J. Environ. Monit. 2005 7 2 89
P. Quevauviller et al. Science-policy integration needs in support of the implementation of the EU Water Framework Directive Environ. Sci. Policy 2005 8 3 203
J. Grath et al. Report on EU guidance on groundwater monitoring developed under the common implementation strategy of the water framework directive J. Environ. Monit. 2007 9 11 1162 1175
J. Harris J. C. Loftis R. H. Montgomery Statistical methods for characterizing ground-water quality Ground Water 1987 25 2 185 193
R. M. Hirsch J. R. Slack R. A. Smith Techniques of trend analysis for monthly water quality data Water Resour. Res. 1982 18 1 107 121
R. M. Hirsch R. B. Alexander R. A. Smith Selection of methods for the detection and estimation of trends in water quality Water Resour. Res. 1991 27 5 803 813
J. C. Loftis C. H. Taylor P. L. Chapman Multivariate tests for trend in water quality Water Resour. Res. 1991 27 7 1419 1429
S. S. Shapiro M. B. Wilk An analysis of variance test for normality (complete samples) Biometrika 1965 52 591 611
S. S. Shapiro R. S. Francia An approximate analysis of variance test for normality J. Am. Stat. Assoc. 1972 67 337 215 216
J. R. Carr, Numerical Analysis for the Geological Sciences, Prentice Hall, Englewood Cliffs, NJ, 1995, p. 592
M. G. Kendall, Rank Correlation Methods, Charles Griffin & Company, London, 1948
H. B. Mann Nonparametric tests against trend Econimetrica 1945 13 245 259
D. R. Helsel and R. M. Hirsch, Statistical methods in water resources, Studies in Environmental Science, Elsevier, Amsterdam, The Netherlands, 3rd edn, 1995, vol. 49, p. 529
S. Yue P. Pilon G. Cavadias Power of the Mann-Kendall and Spearman's rho tests for detecting monotonic trends in hydrological series J. Hydrol. (Amsterdam, Neth.) 2002 259 1-4 254 271
P. Schlosser et al. Tritium/3He Dating of Shallow Groundwater Earth Planet. Sci. Lett. 1988 89 3-4 353 362
E. Busenberg L. N. Plummer Use of chlorofluorocarbons (CCl3F and CCl2F2) as hydrologic tracers and age-dating tools: the alluvium and terrace system of Central Oklahoma Water Resour. Res. 1992 28 9 2257 2283
E. Busenberg L. N. Plummer Dating young groundwater with sulfur hexafluoride: natural and anthropogenic sources of sulfur hexafluoride Water Resour. Res. 2000 36 10 3011 3030
J. L. Pinault H. Pauwels C. Cann Inverse modeling of the hydrological and the hydrochemical behavior of hydrosystems: application to nitrate transport and denitrification Water Resour. Res. 2001 37 8 2179
J. L. Pinault, Manuel utilisateur de TEMPO: logiciel de traitement et de modélisation des séries temporelles en hydrogéologie et en hydrogéochemie, Projet Modhydro. Rap. BRGM/RP-51459, BRGM, Orleans, 2001, p. 221
H. P. Broers, Strategies for regional groundwater quality monitoring, in PhD thesis. Fysische geografie, Utrecht University, Utrecht, 2002, p. 231
H. P. Broers The spatial distribution of groundwater age for different geohydrological situations in the Netherlands: implications for groundwater quality monitoring at the regional scale J. Hydrol (Amsterdam, Neth.) 2004 299 1-2 84 106
A. Dassargues and A. Monjoie, The Chalk in Belgium, in The Hydrogeology of the Chalk of North-West Europe, ed., R. A. Downing, M. Price, and, G. P. Jones, Oxford Science Publ., Oxford, 1993, pp. 153-269
C. Mouvet, et al., PEGASE. Pesticides in European Groundwaters: detailed study of representative aquifers and simulation of possible evolution scenarios, in Final Report of the European Project #EVK1-CT1990-00028. BRGM/RP-52897-FR, ed., I. G. Dubus, and, C. Mouvet, 2004
J. L. Pinault I. G. Dubus Stationary and non-stationary autoregressive processes with external inputs for predicting trends in water quality J. Contam. Hydrol. 2008 100 1-2 22 29
N. Baran C. Mouvet P. Négrel Hydrodynamic and geochemical constraints on pesticide concentrations in the groundwater of an agricultural catchment (Brévilles, France) Environ. Pollut. 2007 148 3 729 738
F. Steinman, Beobachtung der Grundwasserbeschaffenheit in Schleswig-Holstein: Trendmessnetz 1995-2000, Landesamt für Natur und Umwelt des Landes Schleswig-Holstein, Flintbek, Germany, 2002, p. 54
A. Visser H. P. Broers M. F. P. Bierkens Dating degassed groundwater with 3H/3He Water Resour. Res. 2007 43 10 WR10434
A. Visser et al. Degassing of 3H/3He, CFCs and SF6 by denitrification: measurements and two-phase transport simulations J. Contam. Hydrol. 2009 103 3-4 206 218
S. Roulier et al. Controls on atrazine leaching through a soil-unsaturated fractured limestone sequence at Brevilles, France J. Contam. Hydrol. 2006 84 1-2 81 105
A. Gutierrez N. Baran Long-term transfer of diffuse pollution at catchment scale: respective roles of soil, and the unsaturated and saturated zones (Brévilles, France) J. Hydrol. (Amsterdam, Neth.) 2009 369 3-4 381 391
J. C. Vogel, Investigation of Groundwater Flow with Radiocarbon, in IAEA Symposium on Isotopes in Hydrology, 14-18 November 1966, IAEA, Vienna, Austria, 1967
A. W. Harbaugh, et al., MODFLOW-2000, the U.S. Geological Survey Modular Ground-Water Model - User Guide to Modularization Concepts and the Ground-Water Flow Process. USGS Open-File Report 00-92, 2000, p. 121
C. Zheng and P. P. Wang, MT3DMS: A Modular Three-Dimensional Multispecies Transport Model for Simulation of Advection, Dispersion, and Chemical Reactions of Contaminants in Groundwater Systems. Documentation and User's Guide, Department of Geological Sciences, University of Alabama, Alabama, 1999, p. 220
B. Van der Grift and C. G. E. M. Van Beek, Hardness of Abstracted Groundwater: Indicative Predictions (in Dutch), Kiwa, Nieuwegein, the Netherlands, 1996
J. imůnek, M. ejna and M. T. Van Genuchten, The Hydrus-1D Software Package for Simulating the One-Dimensional Movement of Water, Heat and Multiple Solutes in Variable-Saturated Media, Version 2, U.S. Salinity Laboratory, Riverside, CA, USA, 1998
G. Carabin A. Dassargues Modeling groundwater with ocean and river Interaction Water Resour. Res. 1999 35 8 2347 2358
P. Orban, Solute Transport Modelling at the Groundwater Body Scale: Nitrate Trends Assessment in the Geer basin (Belgium), PhD Thesis, 2009, Faculty of Applied Sciences, University of Liège, Liège, p. 219
S. Brouyère et al. The hybrid finite element mixing cell method: a new flexible method for modelling mine ground water problems Mine Water and the Environment 2009 28 2 102 114
N. J. Jarvis, The MACRO Model (version 3.1). Technical Description and Sample Simulations, Reports and Dissertations 19, Department of Soil Sciences, Swedish University of Agricultural Sciences, Uppsala, Sweden, 1994
D. Thiéry, Logiciel MARTHE - Modélisation d'Aquifére avec maillage Rectangulaire, Transport et HydrodynamiquE, version 4.3. BRGM report R 38210, BRGM, Orleans, France, 1990, p. 330
EU, Common Implementation Strategy for the Water Framework Directive (2000/60/EC), Guidance Document No. 15, Guidance on Groundwater Monitoring. Technical Report - 002-2007, Office for Official Publications of the European Communities, Luxembourg, 2007, p. 54
A. J. Tesoriero et al. Linking ground-water age and chemistry data along flow paths: implications for trends and transformations of nitrate and pesticides J. Contam. Hydrol. 2007 94 1-2 139
K. R. Burow J. L. Shelton N. M. Dubrovsky Regional nitrate and pesticide trends in ground water in the eastern San Joaquin Valley, California J. Environ. Qual. 2008 37 S5 249 263
D. A. Saad Agriculture-related trends in groundwater quality of the glacial deposits aquifer, central Wisconsin J. Environ. Qual. 2008 37 S5 209 225
M. G. Rupert Decadal-scale changes of nitrate in ground water of the United States, 1988-2004 J. Environ. Qual. 2008 37 S5 240 248
L. M. Debrewer S. W. Ator J. M. Denver Temporal trends in nitrate and selected pesticides in mid-atlantic ground water J Environ. Qual. 2008 37 S5 296 308
H. Behrendt, et al., Nutrient Emissions into River Basins of Germany on the Basis of a Harmonised Procedure, Umweltbundesamt, Berlin, Germany, 2003