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Wat. Res. Vol. 33, No. 14, pp. 30833097, 1999 # 1999 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0043-1354/99/$ - see front matter

REVIEW PAPER MARKER SPECIES FOR IDENTIFYING URBAN GROUNDWATER RECHARGE SOURCES: A REVIEW AND CASE STUDY IN NOTTINGHAM, UK
M MIKE H. BARRETT1*, KEVIN M. HISCOCK2, STEPHEN PEDLEY1*, DAVID N. LERNER3, JOHN H. TELLAM4 and MIKE J. FRENCH5

Robens Centre for Public and Environmental Health, University of Surrey, Guildford Surrey, GU2 5XH, UK; 2School of Environmental Sciences, University of East Anglia, Norwich NR4 7TJ, UK; 3 Groundwater Protection and Restoration Group, University of Sheeld, Mappin Street, Sheeld S1 3JD, UK; 4School of Earth Sciences, University of Birmingham, Edgbaston, Birmingham, B15 2TT UK; 5Department of Environmental Sciences, University of Bradford, Bradford, BD7 1DP UK (First received May 1998; accepted in revised form December 1998) AbstractUrban environments signicantly alter the nature of recharge to underlying aquifers. Direct precipitation is reduced, but additional recharge may result from storm water runo, mains supply leakage and sewer leakage. If urban aquifers are to be eectively and sustainably managed, it is vital that these recharge sources should be identied and quantied. A sound theoretical approach is the use of marker species for identifying the three principal sources of urban recharge (precipitation, mains and sewers). The ideal marker species should be unique to a particular recharge source (irrespective of geographic location), and easily identiable in the groundwater system, enabling quantication of that source. A review of potential markers and a detailed study of the aquifer beneath the city of Nottingham, UK, was unable to nd suitable markers for precipitation and mains leakage. Trihalomethanes, which are chlorination by-products, and so a potential marker of mains water, were hardly detected in either mains or groundwater. More potential markers are available for sewage, including d-limonene, which is a new ingredient in some detergents. For shallow groundwater, the most eective means of identifying sewage recharge was a combination of stable nitrogen isotopes and microbiological indicators; eectively a sewage ``ngerprint''. This study conrms the need for a multi-component approach rather than using individual marker species. Additionally it demonstrates that the impact of sewer leakage on groundwater quality beneath Nottingham is generally not high. # 1999 Elsevier Science Ltd. All rights reserved Key wordsmarker species, urban groundwater, nitrogen isotopes, faecal bacteria, sewage

NOMENCLATURE

SOURCES OF RECHARGE IN URBAN AREAS

AOS CFC EDTA IOS Rspl Rstd STW TeCE TCE TCM THM dD(H2O) d18 OH2O d15 NNO3 d34 SSO4

adsorbable organic sulphur chlorouorocarbon ethylenediaminetetraacetic acid ion-paired organic-bounded sulphur 15 Na14 N ratio of sample 15 Na14 N ratio of air Severn Trent Water plc tetrachloroethene trichloroethene trichloromethane trihalogenated methane Da1 H ratio in water (-) 18 Oa16 O ratio in water (-) 15 Na14 N ratio of dissolved NO3 (-) 34 Sa32 S ratio of dissolved SO4 (-)

*Corresponding author. [Fax: +44-1483-259971; E-mail: m.h.barrett@surrey.ac.uk].

The sources of recharge to rural aquifers were identied by Lerner et al. (1990) as precipitation, rivers and other surface waters, inter-aquifer ows, and irrigation. The same sources exist in urban areas, but their pathways become more complex and other sources are added, including storm water, potable water supplies, and waste water or sewage. These sources and pathways are summarised in Fig. 1. Regional groundwater ows may carry rural groundwater under the city, where urban recharge is superimposed. There is plenty of scope for direct recharge of precipitation through city parks and gardens, and over-irrigation of such amenity areas occurs in many cities, with a consequent increase in recharge. Precipitation which encounters impermeable roofs, roads and car parks can still become recharge, although there is some evidence that

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Fig. 1. Urban recharge sources and pathways.

roads are not completely impermeable (Hollis and Ovenden, 1988). Water can inltrate along the edges of roads and paths, especially if no storm drains exist. There may be local soakaways (Thomson and Foster, 1986), inltration basins or recharge boreholes for stormwater (Appleyard, 1993) and there is a distinct possibility of storm sewers leaking. Water supply can import large quantities of water into a city (Price and Reed, 1989; Lerner, 1990; Foster et al., 1994). For example, the public supply system imports about 650 mm/yr into Nottingham (UK), and supplies to highly developed commercial centres can reach 7000 mm/yr. This water is a potential recharge source, as leakage rates of 25% from water mains are considered commonplace in the UK (Lerner et al., 1982; University of Birmingham, 1984; Lerner et al., 1993; Greswell et al., 1994). Additional recharge routes include leaking sewers (Lerner et al., 1994; Barrett et al., 1997) and deliberate recharge through septic tanks in unsewered areas. The complex and ever-changing urban environment makes it dicult to identify individual recharge sources and pathways, and to estimate their contributions to the overall groundwater balance. Most of the city-wide studies so far have relied upon water balances of the source waters combined with groundwater modelling, to prove and quantify urban recharges (Lerner et al., 1982; Lerner et al., 1993; Greswell et al., 1994). However,

all waters carry solutes, and these may act as markers of recharge sources. The usual chemical approach has been to study the solutes in urban groundwater, and by considering many species together to deduce the most likely origins of the waters. Using this standard hydrochemical approach is time-consuming; it would be extremely useful if a few ``marker'' species could be identied that could then be used to identify and possibly quantify a particular urban recharge source. Although a few studies have found specic chemical species to be useful for specic source identication in specic studies (e.g. Lerner, 1986 in Hong Kong; Butler and Verhagen, 1997 in Pretoria; and Rivers et al., 1996 in Nottingham, UK) it is recognised that ideal markers may well not exist. However, we are not aware that there has been any systematic searches made for such species, and that it would be worthwhile, starting from the chemical composition of particular recharge source waters, to search for ideal markers. Hence, the objectives of the current study were to review the suitability of many chemical species as markers for dierent urban recharges, and to apply the ndings in a particular urban aquifer: the Triassic Sherwood Sandstone of Nottingham (UK). Markers are dened here as species that can be used in isolation to indicate recharge sources. To meet these objectives, a large number of marker species were considered, on the basis of literature reviews and through thorough analyses of samples

Marker species for urban groundwater recharge

Table 1. Potential markers for urban recharge Category Inorganic Group major cations major anions nitrogen species other minor ions metals atmospheric chlorination by-products faecal detergent related industrial faecal microbiological colloidal stable isotopes Species

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Organic

Particulate Isotopes

Ca Mg K Na HCO3 SO4 Cl NO3 NH4 (plus organic nitrogen) B PO4 Sr F Br CN Fe Mn trace metals chlorouorocarbons (CFCs) trihalomethanes (THMs) coprostanol, 1-aminopropanone optical brighteners, EDTA, limonene chlorinated solvents, hydrocarbons etc. E. coli, faecal streptococci, enterovirus, bacteriophage organic, inorganic 2 H 15 N 18 O 35 S

of raw recharge waters and urban groundwater, with the aim of nding one or more species that would be useful in marking, and ideally quantifying, each major recharge source. Consideration was also given as to whether the marker species identied by the study were applicable universally, or only useful in the Nottingham case study.
REVIEW OF POTENTIAL MARKERS AND THEIR ORIGINS

Boron and phosphorus Both B and P are major constituents of many detergents, and so are found in sewage. Tripolyphosphate may be present at up to 30% of total detergent composition. This is used to soften the wash water and also helps break up dirt on fabrics. Boron may be present in the form of sodium perborate, an oxygen bleach used in the UK for over 50 years. This comprises some 515% of total detergent composition. Constraints on the potential use of boron and phosphate as sewage marker species are (a) detergent composition is variable so these species may not always be present, (b) boron and phosphate are not unique to sewage (e.g. they are frequently used in metal working industries (Ford and Tellam, 1994)), and (c) their occurrence and mobility in groundwater is constrained by pH, aecting solubility and sorption (Ford and Tellam, 1994). In the case of problem (b), boron isotope ratios may sometimes be of assistance (e.g. Leenhouts et al., 1998). Other minor ions (Sr, F, Br, CN) Strontium is not particularly associated with urban pollution (Ford and Tellam, 1994) and is naturally present in precipitation and carbonate minerals, and hence groundwaters, at low concentrations. Fluoride is not naturally present in signicant concentrations in groundwaters of the sedimentary aquifers of the UK, due to one or more of the following concentration controls: lack of source, pH dependent sorption and uorite solubility. There is potential for uoride input to groundwater from phosphate fertiliser application or leakage of uorinated drinking water, but sorption and solubility controls will limit the quantitative usefulness of this indicator. Bromide is a conservative ion and is released to the environment in the form of pesticides and through spills and leaks of halogenated organic compounds. It is also often associated with Cl in inorganic salts and in halogenated organic compounds, and may be expected to be present where Cl inputs have occurred. Cl/Br ratios may be of use in some cases

An ideal recharge marker would be an easily analysed solute that was unique to one water source and pathway, at a constant concentration in the source, and be non-reactive in all conditions. Such solutes are rare! Table 1 summarises the groups of solutes that are considered below as potential markers, while Table 2 summarises the potential sources of these solutes in groundwater. Major ions and nitrogen species The major ions in general are of little use as ``ideal'' recharge markers. Not only are they present in all recharge waters, but the cation ratios can change due to ion exchange processes. In addition, HCO3 is likely to be controlled by interaction with the aquifer. Only Cl and SO4 are reasonably conservative, but it will only be in exceptional cases that they will be at distinctive enough concentrations in just one source water to be useful. However, major ion chemistry is very useful as a recharge marker in general. From major ion chemistry, distinctions between urban and rural, pre-industrial or industrial groundwater in a given system may be made. NO3 is classically related to agricultural fertiliser input and so can mark rural, direct recharge, while NH4 is distinctive of sewage. Sewage also contains organic nitrogen, which is rapidly transformed to NH4. Unfortunately both inorganic nitrogen species are redox sensitive, so it is rare to observe widespread NH4 under aerobic conditions since it is oxidised to NO3. Thus, individual nitrogen species and total nitrogen have potential as markers but care is needed in interpretation, which can be aided by the use of 15 N isotope data, as discussed later.

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(Davis et al., 1998). Cyanide is used in various industrial processes (notably bleaching and dyeing), and has the potential to enter urban groundwater through spillage or leakage from sewers. However, it is highly reactive: it was not detected in groundwater samples from the Birmingham (UK) urban aquifer (Ford and Tellam, 1994). Metals (Fe, Mn, trace metals) Metals may be present in urban aquifers as a result of recharge from precipitation, mineral dissolution and industrial activity. Their relatively complicated sorption, complexing and redox chemistry makes them of very limited use as quantitative markers in most systems. Chlorouorocarbons Chlorouorocarbons (CFCs or Freons), a group of halogenated alkane derivatives, are stable, volatile, synthetic compounds that are detectable to about one part in 1015 (by weight) in water and one part in 1012 (by volume) in air (Busenberg and Plummer, 1992). The release of CFCs into the atmosphere is believed to have been roughly proportional to their rate of production, which is known to have increased exponentially from at least 1956 to the mid-1970s (Rowland and Molina, 1975), levelling o since the Montreal Protocol took eect in 1996. CFCs are resistant to microbial degradation in an aerobic hydrological environment and are potentially valuable, but qualitative, tracers of recent (post 1940s) recharge water (Szabo et al., 1996). Since the detection limit for CFCs is extremely low, it is possible to detect recharge mixtures of as little as 0.01% modern water in pre-1940 groundwater. The detection of modern waters is even more sensitive if recharge has been contaminated with CFCs from anthropogenic sources, such as landll sites, in addition to that of the atmosphere (Russell and Thomson, 1983). Thus, even if the CFC content of mains water supplying an urban area is especially dierent to local groundwater recharge, it is unlikely that CFCs could eectively distinguish mains water and sewer leakage from other potential sources of CFCs such as waste disposal sites.

Chlorination by-products Chlorination of groundwater may result in the presence of THMs (trihalogenated methanes) due to the presence of existing organic compounds. THMs are possible mains water marker species and include bromodichloromethane, bromoform (tribromomethane), chloroform (trichloromethane, TCM), dibromochloromethane and dichloroiodomethane. TCM is the most abundant but is also used in industry. Mains water is a major part of domestic sewage and these species may enter groundwater from leaking sewers. A study of the Coventry (UK) aquifer (Burston et al., 1993) showed a mean TCM concentration of 60 mg/l in mains water and concentrations up to 18 mg/l in the raw sewage. The mean deep groundwater concentration in Coventry for TCM was found to be 2.1 mg/l. The study concluded that mains water was the likely source for the TCM in groundwater (the mains water loading being considerably higher than that of sewage), and higher concentrations in groundwater were related to zones of high density of water supply. In an investigation of the water quality in the shallowest levels of the Birmingham urban Triassic Sandstone aquifer (UK), Ford and Tellam (1994) found levels of TCM consistent with the estimate given by Lerner (1986) of 2025% water mains leakage: the public water supply in Birmingham contains organic material from reservoir catchments in Wales.

Faecal organics Coprostanol (a faecal steroid) has been described in the literature as a useful species for determining the degree to which coastal waters have been contaminated by sewage by analysing sediment samples (Hatcher and McGillivary, 1979; Kelly, 1995). Faecal steroids are produced by enteric bacterial reduction of unsaturated sterols in higher animals (Hatcher and McGillivary, 1979). However, coprostanol is not suitable for use in groundwater studies as it is highly hydrophobic and tends to remain within sewage sludge, rather than the liquid portion of the sewage. It is more useful as a means of indicating sewage contamination of coastal waters

Table 2. Sources of possible marker species Atmosphere Majors N species B and PO4 Other minors Metals CFCs THMs Faecal Detergent Industrial Microbiological Colloidal Geological materials Agriculture Mains water Sewage Industrial and commercial sites

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around sewage outfalls by analysing sea oor sediments where sewage sludge may accumulate. Aminopropanone is a species present in human urine and not, as far as is known, produced signicantly by other natural processes. Potentially this could be an extremely useful marker species. A study carried out by the university of liverpool identied 1-aminopropanone in raw sewage and contaminated coastal waters (Fitzsimmons et al., 1995). Future work should be undertaken to analyse groundwater for this species and to establish its persistence and mobility in groundwater; the analytical technique was not available to the researchers during this study. Organics from detergents Optical brighteners and sulphonic acids, sometimes known as uorescent whitening agents, are included in detergents to maintain the whiteness of fabrics and so are potential markers of sewage. Two of the main groups are diaminostilbene disulphonic acid derivatives and distyryl biphenyl derivatives. Two problems with using them as sewage markers are (a) that they constitute just 0.08% of a typical detergent, resulting in typical wash water concentrations of just 10 mg/l prior to dilution in the sewer system (SDIA, 1995), and (b) that they are designed to adsorb to fabrics, lowering the dissolved concentrations further. EDTA (ethylenediaminetetraacetic acid) is a sequestering agent used in washing products to prevent problems such as scale or sediment formation. It generally constitutes less than 5% of detergents. EDTA has been detected in groundwater in the Dresden area of Germany, where its source is contaminated river water that inltrates a sand and gravel aquifer (Grischek et al., 1994). d-limonene (4-isopropenyl-1-methylcyclohexane [common names citrus terpenes, orange terpenes, menthadiene], chemical formula C10H16) is used as an aromatic scenting agent in domestic cleaning products and as a speciality solvent. It is naturally derived from orange peels before they are processed for cattle feed (Nickerson Chemicals, 1997). It is considered harmful by inhalation, in contact with skin and if swallowed. There is a possible risk of irreversible eects and it is a possible carcinogen (Sigma-Aldrich Co. Ltd., 1997), although it is classied as a low hazard in terms of water pollution by the German classication scheme (Klake, 1996). There is debate as to whether dlimonene is readily biodegradable, some workers considering it to be degradable (Nickerson Chemicals, 1997) and others considering it to be as persistent as halogenated hydrocarbons (Klake, 1996). It is currently being marketed as an environmentally friendly (non-ozone depleting) alternative to the chlorinated solvents such as trichloroethylene.

Industrial organics A range of organic pollutants are widely found in urban groundwater, especially chlorinated solvents (e.g. Rivett et al., 1990; Burston et al., 1993). These come from industrial and commercial sites, and usually enter the subsurface because of spills or waste disposal activities. These compounds are likely to be present in the wastewater from such sites, and hence in the sewer system. However, they will not normally be useful as sewage markers because the proven high incidence of spillages provides an alternative entry route to groundwater. Microbiological parameters Since the pioneering work of John Snow (1936) into the transmission of cholera in London, water has been recognised as an eective vehicle for the spread of many gastrointestinal, human pathogens. Yet, despite over 100 years of accumulated knowledge of the transmission of disease by water, waterborne disease is amongst the major causes of human morbidity and mortality. The World Health Organisation (WHO) ``Guidelines for DrinkingWater Quality'' (WHO, 1993) state that control of microbiological contamination is of paramount importance. The most frequently used method for the determination of faecal pollution of a water sample (and hence sewage recharge to groundwater in the urban context) is to test for the presence of faecal indicator bacteria. These are groups of bacteria that are present in high numbers in faeces, but are absent from other sources. Historically, thermotolerant (formerly faecal) coliforms, Escherichia coli, total coliforms and faecal streptococci have been used as indicators. The signicance of these groups of bacteria for the protection of public health has stimulated a considerable amount of research worldwide into their distribution and persistence in the environment (Pedley and Howard, 1997). From these studies it is now clear that many bacteria with the characteristics of total coliforms can be isolated from environmental sources which are free from faecal contamination. However, despite the many limitations associated with the use of faecal indicator bacteria they continue to be the most widely used groups of indicator organisms by the water industry. Viruses, such as enterovirus, may also enter the groundwater system as a result of faecal contamination. These are not generally used as indicator species due to their problematic isolation and quantication. An alternative to standard virus analysis is the use of bacteriophage. These are viruses which infect a host bacteria, enabling easier isolation and quantication. An example is coliphage, a virus that uses E. coli as a host organism. Organic and inorganic colloids Preliminary research has indicated that colloids can be used in provenancing pollution in two main

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ways. Firstly, the chemical composition of the colloids will give a direct indication of source, in a similar way to solutes. Alternatively, highly sorbing colloids can be added to a groundwater sample (a process referred to below as seeding); a period of equilibration follows during which any sorbing solutes present in concentrations below normal analytical detection limits sorb to the colloids; the colloids with their sorbed loads, are recovered and analysed using electron microscopy with an energy dispersive X-ray analysis facility. These methods have previously been applied in the Birmingham urban Triassic Sandstone aquifer (UK) by Kleinert et al. (1995), Tellam et al. (1996) and Stagg et al. (1998). Colloids containing Ni and Cr, and Au and Hg indicated pollution from metalworking and jewellery-working sites respectively: seeding usually resulted in a wider range of metals being identied on the colloids. Although the approach shows promise, too little is known as yet of colloid production processes, colloidsolute interactions, and colloid migration through aquifers. It is unlikely that colloids will provide ideal markers for mains, precipitation or sewage recharge. Stable isotopes The use of the technique of isotope hydrochemistry in hydrogeological systems involves studying the variation in the isotopic composition of dissolved solutes (for example d15 NNO3 , d34 SSO4 ) in order to understand the origin and fate of chemical species in aquifers. This is in contrast to the more commonly applied eld of isotope hydrology, which involves monitoring the isotopic composition of the water molecules (d18 OH2O , dD(H2O)) themselves in order to understand mixing, palaeoclimate, ow mechanisms and other processes pertinent to the water body as a whole. Isotope hydrochemistry relies on the assumption that sources of dissolved solutes have distinct isotopic compositions and that the processes that aect the isotopic distribution do so in a simple, unique fashion. Unfortunately, these conditions are rarely met, meaning that supporting chemical and hydrogeological data are critically important when attempting to interpret stable isotope data. Ideally, for the isotopic composition of dissolved solutes to be used as source identiers, there must be no signicant isotopic fractionation aecting the dissolved solute, or the fractionation needs to be predictable. For example, large fractionations occur during the biologically mediated reduction of nitrate and sulphate, both potentially causing large enrichments in the heavy isotope of the remaining solute. Stable nitrogen isotopes. Variations in the stable isotopic composition of naturally occurring elements result from equilibrium and kinetic fractionation eects during physico-chemical processes (Rivers et al., 1996). Nitrogen has two stable iso-

topes, 15 N and 14 N, and their relative abundances are measured with respect to atmospheric nitrogen. If R is the ratio of the heavier isotope to the lighter isotope, then the relative fractionation is expressed thus: d15 N 1000Rspl aRstd 1 1

where Rspl 15 Na14 N is the ratio of the sample and Rstd 15 Na14 N is the ratio of air. Results are given in deviations of parts per thousand (-); if d15 N is positive, the sample is isotopically heavy, and vice versa, relative to the air standard (d15 N=0-). Nitrogen isotopes may be used to distinguish between dierent pollution sources by comparing the d15 N value of the groundwater to that of the potential recharge sources (Heaton, 1986). Interpretation must be cautious given the overlap between the variable isotopic compositions of potential sources and because of isotopic fractionation during nitrogen transformation processes (as found by Ravenscroft (1983) in the Birmingham aquifer, UK). Processes that aect the nitrogen isotope composition of groundwater nitrate include denitrication and groundwater mixing (Mariotti et al., 1988). Wilson et al. (1994) concluded that the distribution of isotope compositions in the East Midlands, UK, Triassic Sandstone aquifer is controlled by nitrogen inputs from a variety of sources. Figure 2 shows the nitrate-N isotope signatures considered typical of particular recharge sources. Generally, a value of d15 NNO3 >10- is regarded as being indicative that at least some of the nitrogen present in the sample is of a faecal source. In the urban groundwater context, values in excess of this level may be regarded as indicative that recharge from sewage is present. Due to the potential for a number of recharge sources to contribute nitrogen to an aquifer, values lower than 10- do not necessarily indicate the absence of sewage recharge, but may simply result from source mixing.

Fig. 2. Typical ranges of d15 N signatures for various nitrogen sources (after Fairbairn, 1996).

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Stable oxygen, hydrogen and sulphur isotopes. The stable isotopic composition of water oxygen and hydrogen (d18 OH2O and dD(H2O)) in rainfall can provide a conservative tracer for various sources of groundwater recharge. In the context of urban aquifers, if the isotopic composition of mains water imported into an urban district is distinct from the local groundwater signature, then it might be possible to identify mains and sewer leakage. The study by Butler and Verhagen (1997) is a clear demonstration of this approach where the d18 O and dD values of mains water supplying the townships of Pretoria, South Africa, dier from the natural groundwater by some 30 times the standard deviation of measurement, allowing the detection of 5 10% mains water in groundwater. However, a similar isotopic approach by Brennan (1997) applied to the Sherwood Sandstone aquifer beneath the City of Liverpool (UK) showed that it was not possible to distinguish between groundwater and mains water due to their similar isotopic compositions. Mixing of isotopically enriched waters with relatively depleted groundwaters did, however, reveal that leakage was occurring from a canal in the city centre. On a global basis the ranges of isotopic compositions of sulphate in the various potential recharge sources show considerable overlap. For example, rainfall has been recorded as having a d34 SSO4 range of 020- and evaporites as having a range of 832- (Krothe and Libra, 1983; Nriagu et al., 1991). However, locally these ranges are often more restricted. For example, in the Birmingham urban Triassic Sandstone aquifer (UK) modern precipitation derived sulphate (d15 SSO4 =+1.27.1-; d15 OSO4 =+11.513.2-) can be distinguished from local building material derived sulphate (d15 SSO4 =+0.413.8-; d15 OSO4 =+12.620.7-) (Tellam et al., 1994; Hughes, 1998): although this may indicate that the isotopic composition of sulphate might enable precipitation inputs to be quantied, industrial acids, which are extensively used in Birmingham, have similar isotopic signatures to precipitation. In addition, although simple dissolution will not aect the isotopic signatures signicantly, redox reactions can lead to signicant fractionation which is often not quantitatively predictable. Overall, the results in the Birmingham urban aquifer study indicate that the main sources of sulphate are preindustrial precipitation, oxidation of pyrite from the Quaternary deposits overlying the aquifer, Triassic evaporites/evaporite derivatives, industrial H2SO4, and a general isotopically enriched urban signature (similar to that found in groundwater beneath Liverpool (UK) by Barker, 1996) which is not resolvable into specic sources (Hughes, 1998). Sewage, as such, was not detectable as a source (Hughes, 1998).

NOTTINGHAM AQUIFER CASE STUDY

Hydrogeology and sampling methods The City of Nottingham was chosen as a study area as it has been a major industrial city since the 18th century, encompassing pharmaceutical and manufacturing industries, and as such should illustrate the eects of long-term urbanisation on groundwater. The Triassic Sherwood Sandstone Group comprises the main aquifer beneath the city, underlain by Permian Limestone to the west and overlain by the Triassic Mercia Mudstone Group to the south and east (Charsley et al., 1990). Figure 3 shows the geology and hydrogeology of the Nottingham study area. Beneath much of the urban area, the aquifer is unconned with thin or no cover of Quaternary deposits. Depths to groundwater vary from 25 m in the Leen and Trent valleys (west and south of the urban area) to in excess of 50 m beneath the northeastern (Daybrook) urban area. The major industrial area is Basford in the Leen valley. Deep groundwater samples for this study were obtained from industrial and public water supply abstraction boreholes. All available sites in the city were sampled (20 industrial and 1 public water supply boreholes). There are two important points to be made regarding the deep borehole sites; the boreholes generally penetrate a considerable thickness of aquifer resulting in pumped samples of mixed groundwater over this interval and, secondly, they may provide ``biased'' samples reecting onsite activities. Shallow groundwater was obtained from both the urban and rural areas. These samples were intended to provide detailed chemical information on recently recharged waters and hence the nature of their recharge sources. In the city, a limited number of sampling points were available in a network of caves. A total of more than 400 caves are known in the Sherwood Sandstone beneath the city centre and all are man-made. The caves used in this study were generally cut as storerooms and cellars and may date back 750 years. The caves provided two means of sampling; some contain shallow wells and the oors of others have been ooded by groundwater. Two points should be noted: that the water sampled has been exposed to the atmosphere which may have resulted in degassing by volatile organics and carbon dioxide leading to non-representative samples with raised pH; and that the ooding of the cave oors suggests that groundwater levels in some city centre locations are currently higher than at the time of cave construction, before signicant groundwater abstraction, possibly demonstrating that current articial urban recharges are greater than natural recharges in these areas. To obtain more representative shallow groundwater samples reecting urban (non-industrial) recharges, a network of shallow boreholes was

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installed. The criteria for site selection were that the sampling area should be residential, the depth to groundwater should be shallow, the aquifer should be unconned and there should be access for a drilling rig with minimal inconvenience to the public. The only area to comply with the above criteria was the Meadows, a 1970s housing development (built in place of, and adjacent to, late 19th century terraced housing). The site is on the Trent ood plain, south of Nottingham Castle and immediately to the west of the city centre. Depths to groundwater are shallow (generally 25 m). The site is not ideal as many of the boreholes are located in the river sands and gravels and made ground immediately overlying the Sherwood Sandstone (thought to

be in hydrogeologic continuity), rather than the Sandstone itself, and is hydrogeologically complex, being located in a regional groundwater discharge zone, but in an area where river bank inltration from the Trent is possible along the southern margin. A network of 11 boreholes was installed within an area of 1 km2. In Nottingham, mains water supply is mostly obtained from groundwater, the public water supply boreholes being located in the rural area (both conned and unconned) to the north and east of the city. The only treatment prior to supply is chlorination (some sources are blended to reduce nitrate levels). The only additional source is the River Derwent in Derbyshire to the north west of the city.

Fig. 3. Geology and hydrogeology of the Nottingham study area.

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For the purpose of this study, mains water quality data were provided by Severn Trent Water plc (STW), precipitation was sampled at Environment Agency rain gauge stations in and around Nottingham and ltered raw sewage samples were taken from the entrance to Stoke Bardolph sewage works (which serves the entire city of Nottingham and is located to the east of the city) and analysed at the STW laboratories.

RESULTS AND DISCUSSION

Markers in source waters Table 3 summarises the results of the analysis of the three source waters, precipitation, mains and sewage. In Nottingham's raw sewage, boron was detected at up to 1.7 mg/l and phosphorus at up to 10.7 mg/ l as PO4 (and also at 0.8 mg/l in precipitation). Considering likely dilution eects in groundwater, the low level of boron in raw sewage makes this an unsuitable marker species for Nottingham. Phosphorus is present at higher levels, but its solubility and mobility is sensitive to the pH conditions of the groundwater, again making it an unsuitable marker species. The raw sewage analysed was found to contain no CN, and Ag at just 40 mg/l, despite both species being on the list of compounds licensed for discharge by industry to sewers by STW. Faecal coliforms were detected at high (although variable) levels within the raw sewage. Analyses for individual species within the raw sewage was not carried out. THMs (given as total THMs) were frequently detected in mains water with total THMs up to 68 mg/l with a mean concentration of 21 mg/l. Chloroform is present in the sewage samples analysed at up to 6 mg/l. These values are three times lower than the corresponding THM levels found in the mains water and raw sewage of Coventry (UK). The mean level of THMs in Coventry's groundwater (where detected) resulting largely from mains water leakage was just 2.1 mg/l (Burston et al., 1993). A similar factor of dilution in the

Markers selected for analysis On the basis of the above review, and the analytical facilities available to the project team, a limited number of species were selected for analysis. Some were analysed for in all water samples, and some only in limited reconnaissance studies. No markers were identied for precipitation recharge. The THMs, particularly TCM, were the only species that showed any likelihood of marking mains water. A substantial number of potential markers were tested for sewage, including detergent components (B, P, d-limonene, sulphonic acids), industrial euents (Ag, toluene, TeCE), and microbiological species (E. coli, faecal streptococci, enteroviruses, and bacteriophage). In addition, major ions and nitrogen species were analysed to provide data for a parallel study applying a multisolute balancing approach to quantify recharges (Yang et al., 1997). Analysis for nitrogen isotope composition of groundwater samples (deep and shallow) was carried out at the University of East Anglia in order to indicate the presence of sewage recharge.

Table 3. Potential marker species in Nottingham's source waters. =not measured; nd=not detected; nq=not quantied; tr=trace. Precipitationa Species Ca Mg Na K Cl SO4 HCO3 NO3-N NH4-N Org N B P Ag CN CHCl3d IOS d-limonene Toluened TeCEd Faecal coliformse
a b

Mainsb Detects (%) 100 100 100 94 100 94 100 100 0 10 17 73 Mean, range (mg/l) 43, 2274 21, 7.042 15, 5.463 2.9, tr5.9 31, 1476 54, tr122 137, 74238 15, 2.930 nd 0.05, tr0.05 0.06, tr0.06 21, 168 Detects (%) 100 100 100 100 100 100 100 0 100 100 100 100 100 0 50 50 100 100 100

Sewagec Mean, range (mg/l) 81, 6399 31, 2141 210, 157289 18, 1324 315, 200386 115, 69178 271, 198344 nd 30, 2241 19.15, 14.124.2 1.3, 1.01.7 6.9, 410.7 0.04, nd nq, tr6 nq 104, 14215 28, 1063 715, 0.22.086

Detects (%) 100 100 100 83 100 100 100 100 67

Mean, range (mg/l) 6.7, 1.611.6 1.7, 0.62.3 7.1, 4.48.6 3.2, tr5.5 12.4, 8.215.1 18.9, 12.930.6 8.7, 5.317.3 5.5, 2.211.1 0.52, 0.360.77

6 samples from dierent sites. Averaged results over 12 months from 20 supply zones. c 4 samples, 1 location. d mg/l. e Thousand cfu/100 ml (individual species not analysed).

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Nottingham aquifer would result in groundwater concentrations below detection levels. The nitrate-nitrogen isotopic values for mains water was sampled at three locations and gave a compositional range from 5.2 to 9.5-, similar in range to the deep urban unconned groundwaters (2.8 to 9.5- in a second sampling round). Samples of precipitation collected from eight locations around Nottingham gave d15 NNO3 values from 3.6 to 8.7-, again similar to the deep groundwaters. Raw sewage was sampled at Stoke Bardolph sewage works on 2 occasions and gave a mean value of 5.3- for dissolved nitrate. From these data it is evident that mains and sewer water samples have isotopic signatures typical of an agronomic source for the nitrate, and that this is explained by the fact that groundwater is supplied by boreholes located in the rural area outside the city. Toluene was detected in all raw sewage samples, but as a common industrial contaminant (as a solvent and a component of petroleum compounds), its presence in groundwater is not sucient to indicate sewage recharge. TeCE was also found to be present in all the sewage samples, but, like toluene, is also a common industrial contaminant. d-limonene was detected, although not quantied, in 50% of the raw sewage samples. This compound does not have a long history of industrial use (unlike many other hydrocarbon solvents) and is more likely to be a useful marker of modern sewage recharge to groundwater.

The raw sewage samples were analysed for total faecal coliforms (individual species were not quantied). Concentrations were generally high, but uctuated over several orders of magnitude. Faecal coliforms are unlikely to have any other major sources in the urban environment other than sewage and hence may be regarded as useful markers of sewage recharge. Limitations on bacterial survival in the subsurface constrain the use of faecal coliforms as the sole indicators of sewage recharge; their presence indicates likely sewage recharge, but their absence does not necessarily indicate that sewage recharge is not occurring. Markers in groundwaters Table 4 summarises the analyses of groundwater with respect to the potential marker species listed in Table 3. In Nottingham's deep groundwater, neither B nor P are detected. In the cave water samples, P is detected in all samples, at up to 9.7 mg/l, but in the shallow Meadows groundwaters P is rarely present (maximum concentration of 0.3 mg/l). No analyses for B were performed in these waters. The nondetection of P in the deep urban unconned groundwaters is likely to be a result of either dilution from the recharge water to levels below detection limits, or as a result of the relatively high pH of the Nottingham aquifer (generally 78). The detections in the Meadows area may be a result of the lower pH conditions of the shallow groundwaters (generally 6.87.2). It is not surprising that

Table 4. Potential marker species in Nottingham's groundwaters. =not measured; nd=not detected; nq=not quantied. Cavesa Species Ca Mg Na K Cl SO4 HCO3 NO3-N NH4-N Org N B P Ag CHCl3d IOSf d-limonene Toluened TeCEd E. colie Faecal streptococci Enterovirus Bacteriophage
a b

Meadowsb Detects (%) 100 100 100 100 100 100 100 100 45 23 0 0 27 55 45 100 100 0 45 Mean, range (mg/l) 146, 88268 61, 3278 36, 1059 8.4, 512 55, 19112 152, 64205 441, 332703 10, 2.329 0.2, 004 0.1, 00.3 nd nd nq 34, 061 16, 058 29, 1160 80, 2180 nd nq, 01

Deep urban unconnedc Detects (%) 100 100 100 100 100 100 100 100 27 8 0 8 0 81 96 Mean, range (mg/l) 96, 39305 50, 23144 66, 9531 5.6, 1.322 141, 341318 126, 46313 288, 150523 13, 6.135 0.3, 00.7 nq, 00.02 nd nq nq nq nq

Detects (%) 100 100 100 100 100 100 100 90 100 100 100 0 10 20 20 30 0

Mean, range (mg/l) 59, 4374 39, 2050 38, 1352 35, 1952 82, 25198 102, 84120 210, 49307 13, 3.224 0.7, 0.41.2 1.1, 0.12.3 3.5, 0.79.7 nd nq nq 5.1, 1.28.9 5.4, 1.010.3 nd

10 samples, 4 sites. 42 samples, 11 sites (11 samples for microbes and organic compounds). c 62 samples, 17 sites (26 samples for organic compounds). d mg/l. e mpn/100 ml (most probable number/100 ml). f IOS=ion paired organic bound sulphur.

Marker species for urban groundwater recharge

Table 5. Microbiology of shallow groundwater in the Meadows Site A B C D E F G H I J K
a

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Total coliforms mpn/100 ml) 13 170 5 540 910 4 110 160 1 13 9

E. coli (mpn/100 ml) 13 20 5 22 1 2 75 160 1 13 9

Faecal streptococci (mpn/100 ml) 9 33 2 9 180 160 160 160 2 3 160

Coliphage (pfu/ml)a 0 1 1 1 0 1 0 0 0 1 0

Enterovirus (pfu/10 l) 0 0 0 0 0 0 0 0 0 0 0

pfu/ml (plaque forming units/ml).

no detections of Ag in groundwater were made, even in the shallow Meadows area, given the low concentrations in raw sewage. Analyses for microbiological species were not carried out for the deep groundwaters (positive detections in depth-mixed samples were considered unlikely even if faecal coliforms were present in surface recharge). Results for the shallow waters showed high levels of faecal coliforms (and the frequent presence of coliphage) in the Meadows area, strongly indicative of a sewage recharge source. No faecal coliforms were detected in the cave waters. The details of the microbiological content of the Meadows waters are shown in Table 5. Nitrogen isotope analysis was carried out on all the groundwaters and the results are shown in Fig. 4 (ranges and median values). Of the deep urban groundwaters, very few samples showed clear evidence for sewage loading (d15 NNO3 >10-). Where values were <10-, neither presence or absence of sewage recharge can be conrmed as the lighter values may simply reect dilution of sewage recharge with other sources of recharge containing nitrogen with a lighter isotopic signature. By contrast, the shallow groundwaters in the residential Meadows area and commercial city centre both show nitrogen isotopic signatures indicative of a sewage source (100% of cave samples and 73% of Meadows samples), although the nitrogen present is

Fig. 4. Ranges of nitrogen isotope signatures (and median values) for deep and shallow groundwaters in Nottingham.

not necessarily exclusively sewage-derived. Compared with the mean d15 N value of 5.3- for raw sewage, the shallow groundwaters show clear evidence of isotopic enrichment. These results conrm the nding of Kreitler (1979) that it is not the sewage itself that is isotopically enriched but the partial volatilisation of ammonia, depleted in 15 N during decomposition of urea in sewage, that causes the residual ammonium and subsequent nitrate to become isotopically heavier during inltration to the water table. The shallow groundwater nitrogen isotope data contrast with the microbiological results, where the cave samples were found to contain no faecal coliforms, whilst counts in the Meadows boreholes were generally high. The sites dier in that the Meadows boreholes penetrate highly permeable unconsolidated materials overlying the Triassic sandstone whereas the city centre caves are located in the sandstone itself (there being no supercial deposits in this area). It is likely that recharge takes considerably longer to reach the water table in the city centre than in the Meadows, possibly leading to reduced microbial concentrations. Very few groundwater samples gave positive detections for THMs, in contrast to the Coventry (UK) survey (Burston et al., 1993). This is not surprising given the low concentrations in the recharge waters of Nottingham, as previously discussed. Inspection of the STW data for individual mains supply zones shows that THM levels in Nottingham's mains water are particularly low (not above detection limits during 1995) in the Meadows area. This is due to the low organic carbon in the source waters (deep groundwater) which results in little formation of THMs during chlorination. Thus, even if mains water were the dominant recharge source in this residential area, THMs would not be a useful recharge marker for Nottingham. A limited set of samples were taken of shallow Meadows groundwater for ion-paired organicbounded sulphur (IOS) analysis, performed at the Technical University of Dresden, Germany. No detections (limit of 50 mg/l) were made (Grischek,

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Mike H. Barrett et al.

Table 6. Combined isotopic, microbiological and d-limonene indicators of sewage contamination of shallow groundwater in the Meadows. Y: yes; this parameter indicates clear sewage contamination (d15 N>10-, total coliforms>100 mpn/100 ml, E. coli>50 mpn/100 ml, faecal streptococci>50 mpn/100 ml). M: maybe; this parameter indicates possible sewage contamination. No: no; this parameter indicates no sewage contamination (d15 N<5-, total coliforms not detected, E. coli not detected, faecal streptococci not detected). U: sewage contamination unlikely. P: sewage contamination possible. C: sewage contamination conrmed roadside, near combined sewer, d-limonene present

1996). Grischek also indicated that, although analyses were not performed, in the context of the IOS results, it was unlikely that adsorbable organic sulphur (AOS) would be present either. These compounds are indicators of uorescent whitening agents in detergents and may be regarded as potential sewage markers. Their absence from the Meadows samples may be as a result of dilution or attenuation as previously discussed. Of the groundwater samples analysed for this study, 5 samples (2 from the shallow city centre caves and 3 from the Meadows) contained detectable levels of d-limonene (although not quantied). It would appear from these results that dlimonene is a potential sewage marker species. However more detailed work is required, including quantication in sewage and groundwater, investigations into the possibility of d-limonene being a degradation product of other compounds and studies of persistence and mobility in groundwater. It is notable that all the detections of d-limonene in Nottingham's shallow groundwater were at sites identied as being contaminated by sewage on the basis of independent isotopic and microbial studies (discussed below). Both toluene and TCE (present in Nottingham's raw sewage) were frequently detected in the groundwaters sampled. However, their extensive use in industry makes them unsuitable as sewage marker species. The fact that they are more frequently detected in Nottingham's deep industrial boreholes than in the shallow groundwaters would suggest a signicant input to groundwater from on-site contamination. A few samples of groundwater were analysed for d34 SSO4 and d18 OSO4 . Preliminary interpretation indicates that the isotopic signatures are very similar to those found in the Birmingham urban aquifer (see above: Hughes, 1998). There appear to be three main sources of SO4: aquifer gypsum; a general urban source (see above); and a light source interpreted in the Birmingham area as resulting from pyrite oxidation in the shallow subsurface. In Nottingham it is possible that the light end member may be associated with sewage recharge; but work is ongoing. The results in the colloid surveys will be described in detail elsewhere. Urban groundwater samples contain greater numbers of colloids than rural groundwaters (Stagg et al., 1997). Organic colloids appear, from limited packer sampling evidence, to decline in concentration with depth in the subsurface, indicating limited vertical penetration of colloids (Stagg et al., submitted). The origin(s) of the organic colloids have yet to be determined. In the Meadows area, organic colloids are much more frequent than in the deep borehole samples (Stagg et al., 1997). One possible source is sewage. Research continues.

roadside, near public lavatories

d-limonene present high Cl high Cl

Sewage impact

d-limonene

Faecal streptococci

E. coli

Total coliforms

d15 N (-)

Depth to water table (m)

Site

A B C D E F G H I J K

Parkland Parkland Parkland Parkland 1970s housing 1970s housing 1970s housing 1970s housing 1970s housing 1970s housing C19th housing

Land use

2.59 3.98 2.23 1.50 4.20 3.48 3.23 3.68 4.00 4.90 5.74

M Y Y Y Y Y Y Y M M Y

M Y M Y Y M Y Y M M M

M M M M M M Y Y M M M

M M M M Y Y Y Y M M Y

No No No Y No Y No No No Y No

U C P C C C C C P P P

d-limonene present

Notes

Marker species for urban groundwater recharge

3095

Combination of markers Overall, a combination of microbiological faecal indicators and nitrogen isotopes were found to give the best indication of the presence or absence of sewage recharge to groundwater. This is demonstrated by Table 6, which summarises the two sets of results for the shallow boreholes in the Meadows area. The table shows that borehole A is unlikely to be contaminated by sewage, C, I, J, K may possibly be contaminated by sewage and B, D, E, F, G and H (55% of sites sampled) are conrmed as being contaminated by sewage. The fact that the two surveys (isotopic and microbiological) broadly corroborate each other suggests that such an approach provides a means of ``ngerprinting'' sewage contamination. The presence of d-limonene in both sewage and shallow groundwater, in the residential Meadows area (at sites D, F, J) and also two of the cave sites, suggests that this also may be a useful sewage marker species. Of the Meadows sites where d-limonene was detected, both D and F are indicated as being contaminated by sewage by means of the microbiological and nitrogen isotopic surveys.

found in both sewage and shallow groundwater in Nottingham, suggesting it may be a good marker for modern sewage. Microbiological and nitrogen isotopes are useful markers of sewage, but are not absolute indicators, due to the die-o of microbiological organisms and the mixing and fractionation processes aecting isotopes. The use of these markers in combination was found to provide the clearest evidence for the presence of sewage in shallow groundwater. Overall, there are still no easy solutions to the problem of identifying recharge sources in urban groundwater. This study conrms the need for a multi-component approach; there are no ideal markers. Other than the general observation of high nitrate values, sewage pollution is dicult to identify. In Nottingham, it appeared that the general impact of sewer leakage on the underlying groundwater quality is not high. This nding is of great signicance in the context of making increased use of urban groundwater resources in the UK.
AcknowledgementsFunding for the study was provided by the Engineering and Physical Sciences Research Council, Severn Trent Water plc, the Environment Agency, Stanton plc, and the Ministry of Agriculture, Fisheries and Food. We are pleased to acknowledge the eld and laboratory assistance provided by Owen Baines and David Hay (University of Bradford), Jane Harris, Paul Mugridge and Kim Stagg (University of Birmingham), Paul Dennis, Nick Feast, Clive Rivers and Jason Fairbairn (University of East Anglia).
REFERENCES

CONCLUSIONS

A wide ranging review has been conducted to nd potential markers for three major sources of urban recharge, namely precipitation, mains leakage and sewer leakage. No markers were identied for precipitation recharge. For mains leakage, the most promising seemed to be the chlorination by-products THMs. However, THM concentrations in Nottingham's mains water were very low, due probably to the fact that the water is derived from a low organic carbon groundwater, such that THMs did not prove useful in this study. For both precipitation and mains water, d34 SSO4 and d18 OSO4 may be useful in other studies, particularly where there is a clear dierence in the isotopic composition of the mains water source compared with the local precipitation (recharge) source, but was not appropriate in this study where the mains water is derived from groundwater recharged in the adjacent areas. A number of potential markers of sewage were identied, originating from human wastes and detergents. A mammalian urinary metabolite, 1aminopropanone, may be suitable but was not analysed for in this project. Boron is a common ingredient of detergents, but was not found at suciently high concentrations in Nottingham's sewage to be of value, but is likely to of use in other studies if the detection limit is low enough and the geochemical conditions appropriate. Caution is needed in the interpretation of B results since it is commonly used in metalworking industries and may enter groundwater from spillages. A new ingredient in detergents is d-limonene and was

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