The Science of the Total Environment 251r252 Ž2000.

9᎐26

River water quality in the Humber catchment: an

introduction using GIS-based mapping and analysis

Takashi Oguchi a , Helen P. Jarvie b, Colin Neal b,U

a
Center for Spatial Information Science, Faculty of Science 5th Building, Uni¨ ersity of Tokyo, Hongo, Bunkyo-ku,
Tokyo 113-0033, Japan
b
Institute of Hydrology, Maclean Building, Crowmarsh Gifford, Wallingford, Oxfordshire OX10 8BB, UK

Accepted 5 January 2000

Abstract

The regional water quality of the Humber catchment was mapped for key inorganic chemical determinands using a
GIS system and an extensive Environment Agency and LOIS monitoring database. The resultant maps revealed the
major factors affecting the general characteristics of regional water quality. Sewage inputs from industrial and
domestic sources account for the high concentration of many determinands in urban areas. The concentrations of
particulate components increase in tidal zones because of sediment trapping and tidal re-suspension effects. Some
determinands also exhibit localized high concentrations related to coal mine drainage, soil pollution caused by past
ore mining, bedrock geology, the agricultural use of fertilizers and the ingression of seawater into the estuary. 䊚 2000
Elsevier Science B.V. All rights reserved.

Keywords: Water quality; Humber catchment; Sewage inputs

1. Introduction tailed water quality data have been collected by

A major objective of the Land-Ocean Interac-
tion Study ŽLOIS. has been the collection, compi-
lation and analysis of river water quality data for
the eastern UK ŽNeal et al., 1997a, 1998a.. Under
the Rivers Research programme ŽRACSŽR.., de-
U
Corresponding author.
establishing a new water quality monitoring net-
work along the major rivers in the eastern UK.
Particular emphasis has been placed on the Hum-
ber catchment, which covers an area of approxi-
mately 24 000 km2 and provides the largest con-
tribution of freshwater to the North Sea of all the
British rivers ŽJarvie et al., 1997a.. Eleven water
quality sampling sites were established with
weekly sampling over a period of 6 years for a

0048-9697r00r$ - see front matter 䊚 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 8 - 9 6 9 7 Ž 0 0 . 0 0 4 1 1 - 3
10 T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26

wide range of chemical determinands, and addi-
tional sampling during periods of high river flow
to provide greater temporal resolution and for
more accurate flux determinations. This has facil-
itated detailed investigation of the hydrochemical
behaviour of the major river systems draining into
the Humber Estuary Že.g. Jarvie et al., 1997b;
Neal et al., 1996, 1997b; Robson and Neal, 1997a.,
but, given the limited number of the LOIS sam-
pling sites, only limited information about regio-
nal variations and extremes in water quality within
such a large catchment area can be derived.
To examine the spatial variability in river water
quality across the Humber catchment, LOIS sci-
entists were granted access to the Environment
Agency’s ŽEA. water quality databases. Water
quality data for major rivers draining into the
North Sea were compiled within an electronic
database at the Institute of Hydrology ŽWater
Information System, WIS. as a part of the LOIS
project ŽMoore, 1997; Tindall and Moore, 1997..
The WIS database brings together data collected
by the EA, including water quality data for rivers,
sewage and trade effluents. For the Humber
catchment, this involved data collected by two EA
regions: YorkshirerNorthumbria Region Žnorth-
ern and central regions of the Humber catchment
draining into the Yorkshire Ouse. and Midlands
Region Žsouthern Humber catchment draining
into the Trent. and their predecessors Žthe Natio-

Fig. 1. Map of the Humber catchment.

 T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26 11

nal Rivers Authority and Water Authorities. for

the period 1986᎐1996. Although the EA data are
characterized by less frequent sampling and fewer
measured determinands than the LOIS data, the
number of the monitoring sites is much larger
and covers a wider and more dense spatial net-
work.
In this study, EA data are used along with the
LOIS data to describe the spatial patterns in river
water quality in the Humber rivers in relation to
catchment characteristics and processes. The
value of regional water quality analysis was de-
monstrated in a case study on the River Tweed
ŽRobson et al., 1996; Robson and Neal, 1997b..
However, until now, no large-scale analysis of
water quality data has been undertaken on the
Humber catchment which has a much larger
drainage area than the Tweed and contributes
greater chemical loads into the North Sea. This
study brings together for the first time all the EA
and LOIS river water quality data for the major
UK rivers network draining into the Humber
Estuary, using GIS-aided mapping and analysis.
The data are presented in the form of an atlas of
water quality maps for the Humber catchment. Fig. 2. EA and LOIS monitoring sites of river water quality in
the Humber catchment.
The work thus extends markedly earlier studies
using a more restricted set of information from
the Harmonised Monitoring Scheme ŽRobson and
chloride, magnesium, sodium, potassium, sul-
Neal, 1997a,b. and preliminary trace element
phate., nutrients Žammonia, total oxidized nitro-
studies ŽNeal et al., 1999. and it provides an
gen, nitrate, nitrite, phosphate., trace elements
important introduction to water quality issues that Žaluminium, barium, boron, cadmium, cobalt,
are relevant to many of the contributions within
copper, iron, lead, manganese, mercury, nickel,
this special issue of Science of the Total En¨ iron-
strontium, zinc., and other major determinands
ment.
Žsuspended solids, dissolved organic carbon..
These determinands were selected because they
represent a wide range of sources and chemical
2. Construction of water quality maps behaviour in river water. Some of the trace ele-
ments have data for both dissolved concentrations
and total acid-available concentrations Ždissolved
Data for the Humber catchment ŽFig. 1. were q acid-available particulate fractions. ŽNeal et al.,
selected from the database using SQL commands 1997b, 1999.; whereas only one or the other may
and ArcView ŽESRI, Redlands, CA, USA.. The be available for some determinands.
total number of river water quality monitoring The average concentration of each determi-
sites within the catchment is 4780 ŽFig. 2.. Of the nand was calculated for monitoring sites with
water quality determinands monitored by the En- more than 50 measurement records. Although
vironment Agency, the chemical determinands water quality at each site varies through time due
chosen for analysis were: major ions Žcalcium, mainly to seasonal changes in flow conditions,
12 T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26
this paper deals with average concentrations com-
puted from all the available data in order to
examine the general characteristics of regional
water quality. The effect of the measurement
season is assumed negligible if a site has more
than 50 measurement records covering several
years’ duration.
The distributions of average determinand con-
centration values were mapped along with the
drainage divide and major stream networks using
ArcView. The stream network was constructed
from a digital elevation model with a grid interval
of 50 m. The projection system used for the maps
is the British National Grid. The concentration
values of each determinand were grouped into six
categories using the ArcView’s natural break cri-
terion, and the values in different groups were
presented using circle symbols with different di-
ameters Že.g. Fig. 3..
The maps generated by these methods revealed
that the data distribution for some determinands
was too sparse to examine regional differences in
concentrations. These determinands were there-
fore excluded from the following analysis. The
average concentrations of both dissolved and to-
tal acid-available fractions of trace elements re-
vealed very similar distributions in most cases and
therefore, only the maps of total concentrations
are presented here. Water quality maps are pre-
sented for the average concentrations of the fol-
lowing determinands: suspended solids, nutrients
Žammonia, total oxidized nitrogen., major ions
Žcalcium, chloride, magnesium, sodium, sulphate.,
and total acid-available trace elements
Žaluminium, boron, cadmium, copper, iron, lead,
nickel, zinc..
3. Characteristics of water quality maps
The water quality maps for the Humber catch-
ment are shown in Figs. 3᎐18 at the end of this
paper. The towns, cities and rivers referred to are
shown in Fig. 1. Investigation of the average
chemical concentrations have revealed the fol-
lowing characteristics in terms of regional water
quality.
3.1. Suspended solids (Fig. 3)
The highest concentrations of suspended solids
occur in: Ž1. the southern industrialrurban areas
including Birmingham, Derby and Stoke on Trent;
Ž2. the northern industrialrurban areas including
Sheffield, York and Leeds; and Ž3. the tidal
reaches along the Humber Estuary including
Goole and its vicinity. Suspended solids concen-
trations are lower in the rural upstream areas
Že.g. the upper reaches of the Rivers Rye, Swale,
Ure, Wharfe, Derwent and Dove..
3.2. Ammonia (Fig. 4)
The highest concentrations of ammonia occur
in the northern and southern industrialrurban
areas. Low concentrations occur in the Humber
Estuary and the rural upstream areas.
3.3. Total oxidized nitrogen (TON) (Fig. 5)
High concentrations of TON occur in the
northern and southern industrialrurban areas as
well as lowlands along the Rivers Trent, Soar,
Tame, Idle, Hull and Foulness. Low concentra-
tions occur in the upper reaches of the Rivers
Swale, Ure, Rye, Wharfe, Aire and Dove.
3.4. Calcium (Fig. 6)
High concentrations occur in north-eastern ar-
eas along the Hull, Derwent, Ouse, Lower Swale,
Lower Ouse and Lower Don. Although the cal-
cium concentration data within the southern
Humber catchment are sparse, this area also
seems to have relatively high calcium concentra-
tions. Low calcium concentrations occur in the
north-west area of the catchment, including the
Upper Swale, Upper Ure, Upper Nidd, Upper
Wharfe and Upper Calder.
3.5. Chloride (Fig. 7)
High concentrations of chloride occur within
the Humber Estuary and the central part of the
 T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26 13

Fig. 3. Map of suspended-solid concentrations for the Humber catchment Žmgrl..

Fig. 4. Map of ammonia concentrations for the Humber catchment Žmgrl..

14 T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26

Fig. 5. Map of total oxidized nitrogen concentrations for the Humber catchment Žmgrl..

Fig. 6. Map of calcium concentrations for the Humber catchment Žmgrl..

T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26 15

Fig. 7. Map of chloride concentrations for the Humber catchment Žmgrl..

Fig. 8. Map of magnesium concentrations for the Humber catchment Žmgrl..

16 T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26

Fig. 9. Map of sulphate concentrations for the Humber catchment Žmgrl..

Fig. 10. Map of aluminium concentrations for the Humber catchment Ž␮grl..
T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26 17

Fig. 11. Map of boron concentrations for the Humber catchment Ž␮grl..

Fig. 12. Map of cadmium concentrations for the Humber catchment Ž␮grl..
18 T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26

Fig. 13. Map of chromium concentrations for the Humber catchment Ž␮grl..

Fig. 14. Map of copper concentrations for the Humber catchment Ž␮grl..
T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26 19

Fig. 15. Map of iron concentrations for the Humber catchment Ž␮grl..

Fig. 16. Map of lead concentrations for the Humber catchment Ž␮grl..
20 T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26

Fig. 17. Map of nickel concentrations for the Humber catchment Ž␮grl..

Fig. 18. Map of zinc concentrations for the Humber catchment Ž␮grl..
 T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26
catchment around Doncaster and Nottingham.
Most of the other areas are characterized by low
chloride concentrations.
3.6. Magnesium (Fig. 8)
High concentrations of magnesium occur in the
Humber Estuary and the northern industrialr
urban areas. There is only very sparse magnesium
data for the southern area of the Humber catch-
ment.
3.7. Sulphate (Fig. 9)
High to medium concentrations of sulphate
occur in the central to southern areas of the
Humber catchment. Low concentrations of sul-
phate occur in northern areas such as the Ouse
catchment.
3.8. Aluminium (Fig. 10)
High concentrations of aluminium occur in the
northern and southern industrialrurban areas.
Low concentrations occur in northern rural areas.
3.9. Boron (Fig. 11)
High concentrations of boron occur within the
Humber Estuary. Low concentrations occur in
northern rural areas.
3.10. Cadmium (Fig. 12)
The characteristics of the cadmium concentra-
tion map are similar to those of suspended solids:
high concentrations of cadmium occur in the
northern and southern industrialrresidential ar-
eas as well as the tidal zone. Low concentrations
of cadmium tend to occur in the rural upper river
reaches. However, the Derwent and Dove catch-
ments are exceptional: despite their rural loca-
tion, these rivers exhibit high concentrations of
cadmium.
3.11. Chromium (Fig. 13)
Chromium concentrations show a similar dis-
tribution to suspended solids.
21
3.12. Copper (Fig. 14)
Copper concentrations show a similar distribu-
tion to suspended solids, except for low concen-
trations along the River Rother.
3.13. Iron (Fig. 15)
Iron concentrations show a similar distribution
to suspended solids; however, within South York-
shire a discrepancy arises on the Rivers Aire and
Don: the Aire exhibits high suspended sediment
concentrations but relatively low Fe concentra-
tions, whereas the Don has very high Fe and high
suspended sediment concentrations.
3.14. Lead (Fig. 16)
Lead concentrations show a similar distribution
to suspended solids, except for high concentra-
tions along the Swale and the Ure.
3.15. Nickel (Fig. 17)
Nickel concentrations show a similar distribu-
tion to copper except for low concentrations in
the tidal zone.
3.16. Zinc (Fig. 18)
Zinc concentrations show a similar distribution
to nickel, apart from a high concentration around
Chesterfield.
4. Discussion
The chemical concentration maps demonstrate
a high variability in water quality for many de-
terminands across the Humber catchment. All the
determinands shown in Figs. 3᎐18 except for cal-
cium, chloride and magnesium, show higher con-
centrations in the large industrialrurban areas to
the north of the Humber catchment Žparticularly
the LeedsrBradford and SheffieldrDoncaster ur-
ban agglomerations in South Yorkshire. and to
the south Žparticularly around Birmingham in the
22 T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26
English Midlands.. The high concentrations within
these areas can be attributed to sewage dis-
charges and industrial effluents, which have been
found to have a major impact on river water
quality across the Humber catchment Že.g. Neal
et al., 1996, 1997b, 1998b.. More detailed results
are discussed in the following sections related to:
Ž1. trace metals and suspended solids; Ž2. nutri-
ents; and Ž3. major ions and boron.
4.1. Trace metals and suspended solids
Most of the trace metals displayed in this study
show very high concentrations clustered in the
River Tame to the far south of the Humber
catchment, which drains Birmingham and the
‘Black Country’. Chromium, nickel and zinc ex-
hibit particularly high concentrations in the Tame
relative to the rest of the Humber catchment, and
have a primarily industrial source. Industry in this
area has been dominated by metallurgical activity,
particularly iron and steel production in the Black
Country to the west of Birmingham, and non-fer-
rous metal working within Birmingham, including
manufacture, smelting, forging, casting, electro-
plating, drawing and wire manufacture, anodizing
and precious metal working ŽFord and Tellum,
1994.. Chromium, copper and nickel also show
secondary concentration clusters around the in-
dustrial agglomerations of South Yorkshire. High
suspended solids concentrations also occur within
the urban areas of the central and southern
Humber catchment, suggesting that domestic and
industrial effluents provide a major source of
suspended solids to the Humber rivers.
Cadmium, chromium, copper, iron and lead
have high concentrations in the tidal zone Žthe
Humber Estuary and the tidal reaches of the
Rivers Ouse, Aire, Don and Trent., and show a
similar distribution to suspended solids. Compar-
isons of total acid-available concentrations and
dissolved concentrations of these trace elements
demonstrate a high acid-available particulate
component within the total trace element concen-
tration. These trace elements are therefore pre-
dominantly carried in particulate form and are
thus subject to sediment transport effects. The
Humber estuary has provided a sink for sedi-
ments contaminated by trace elements from in-
dustrial activity over many years ŽMillward et al.,
1995., and water and sediment transport mecha-
nisms within the tidal zone actively prevent the
escape of sediments ŽSalomons and Forstner,
1984.. These highly contaminated sediments
trapped within the tidal zone are subject to fur-
ther accumulation and cyclical deposition and
resuspension, producing the high suspended solids
concentrations and high concentrations of
cadmium, chromium, copper, ion and lead across
the Humber estuary and tidal river reaches. Al-
though no data are available for aluminium con-
centrations in the tidal zone ŽFig. 10., the concen-
trations there would be expected to be high, as
aluminium also has a high particulaterdissolved
ratio, and will thus be subject to the same tidal
sediment trapping and mobilization effects.
High iron concentrations are found within the
central part of the Humber catchment, particu-
larly in the Don catchment in South Yorkshire,
and may be related to the discharge of mine
drainage into the local river systems ŽYounger,
1997.. Ferruginous mine drainage results from
the oxidation of pyrite within the coal measures
and associated strata and the removal of the
oxidation products by inflowing groundwater
ŽFrost, 1979.. In recent years, there has been
increasing concern about mine drainage, with the
decline of the British coal mining industry, the
widespread closure of mines and the cessation of
mine dewatering. Flooding of mined voids and
discharge of ferruginous waters from the aban-
doned mines has become a major source of water
pollution in South Yorkshire ŽNRA, 1996..
Anomalously high concentrations of cadmium,
lead and zinc occur in certain rural locations:
cadmium and lead are found in abundance in
Derbyshire ŽRivers Derwent and Dove., lead in
North Yorkshire Žin the upper Swale and Ure.,
and zinc in Derbyshire around Chesterfield. These
areas correspond to the locations of ore mining,
which culminated during the Industrial Revolu-
tion. The ore mining activity was localized, where
veins rich in galena Žlead sulfide. and blende Žzinc
sulfide. were abundant within the Lower Car-
boniferous rock ŽJarvie et al., 1997a.. The mining
fields of Derbyshire and North Yorkshire are
 T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26
characterized by large cadmium storage in flood-
plain sediments ŽBradley and Cox, 1986; Macklin
et al., 1997; Neal et al., 1998b.. Although zinc was
one of the major products from the both the
Derbyshire and Yorkshire Mining Fields, the map
of zinc concentration shows elevated concentra-
tions in only one area of Derbyshire. This obser-
vation may reflect that the zinc contents in the
polluted soils of British mining fields are much
lower than their lead contents ŽLewin and Mack-
lin, 1987..
4.2. Nutrients: total oxidized nitrogen and ammonia
The high density of sites where total oxidized
nitrogen ŽTON. is monitored makes it difficult to
distinguish detailed patterns in concentration ŽFig.
5.. However, it is possible to identify two areas of
elevated TON concentrations in the urban and
industrial regions and lowland agricultural areas
with relatively low population density, particularly
the Vales of Trent and Ouse, the Isle of Axholme
and the low-lying coastal plain of Humberside. In
the urban areas, high TON concentrations reflect
input of nitrogenous sewage effluents. The low-
lands in the Humber catchment are extensively
used for agriculture such as the production of
wheat, corn, potato and sugar beat, requiring the
use of nitrogenous fertilizers ŽJarvie et al., 1997a..
The highest concentrations of ammonia are
clustered in the urban areas of South Yorkshire
and the Midlands. However, unlike TON, there
are only low concentrations of ammonia in the
lower Vale of Ouse and Trent and other major
agricultural areas, indicating the agricultural
runoff is not a major source of ammonia. A major
source of ammonia in river systems is sewage
effluent ŽMcNeely et al., 1979; Jarvie et al., 1998..
Although ammonia is measured in the dissolved
phase, ammonia concentration distributions are
very similar to those of suspended solids, with the
exception of low ammonia concentrations in the
tidal reaches, where suspended solids concentra-
tions are high.
4.3. Major ions and boron
Boron, chloride, and magnesium are abundant
23
in seawater and therefore show very high concen-
trations in the Humber Estuary, owing to mixing
of seawater with the river water from the Humber
catchment. There are high concentrations of cal-
cium within the Humber Estuary also originating
from a seawater source; however, riverine con-
centrations of calcium exceed the estuarine con-
centrations in several places. No data are avail-
able for estuarine concentrations of sulphate.
However, given known composition of seawater
ŽBurton, 1976., elevated concentrations of sul-
phate would be expected in the estuary. Boron,
chloride, calcium and magnesium are all predomi-
nantly found within the dissolved phase Že.g. Neal
et al., 1998b. and therefore are not related to
sediment-associated tidal re-suspension effects.
Chloride also occurs in abundance around
Doncaster and Nottingham in the central region
of the Humber catchment. High chloride concen-
trations can be attributed to coal mine drainage
ŽYounger, 1997.. The Carboniferous rocks within
the region, which include the Coal Measures,
have saline groundwaters, originating from the
diagenesis of marine and brackish waters ŽAllen
Dowing and Howitt, 1969., and so the high chlo-
ride concentrations in mine drainage may repre-
sent relict seawater.
The distribution of sites in the non-tidal rivers
where boron is measured are very sparse. How-
ever, there appears to be a distinction between
the high concentrations to the south of the Hum-
ber catchment, and the low concentrations to the
rural north of the catchment. The major source of
boron in river water is sewage effluent, particu-
larly the soluble boron-containing materials used
in washing powders and detergents ŽNeal et al.,
1998b.. However, the relatively high concentra-
tions of boron in the Rivers Rother and Don may
reflect relict seawater from mine drainage.
The distribution of calcium concentrations is
strongly dependent on geology and weathering of
parent materials. The lowest concentrations of
calcium occur in the upper river reaches to the
north-west of the Humber catchment. These rivers
drain the predominantly base-poor carboniferous
catchments composed of Millstone Grit and Coal
Measure Shales. High calcium concentrations oc-
cur in areas underlain by calcareous Permian,
24 T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26

Triassic, Jurassic and Cretaceous sedimentary
rocks. For example, some of the highest concen-
trations of calcium are found on the River Hull
which drains the Cretaceous chalk of the North
Yorkshire Wolds ŽJarvie et al., 1997a.. Magne-
sium in the non-tidal rivers shows a similar dis-
tribution to calcium, with the exception of the
Rivers Derwent and Hull, which have low magne-
sium concentrations, reflecting the mineral com-
position of the Cretaceous Chalk. The relatively
high concentrations of calcium and magnesium in
the central Humber catchment may reflect a relict
seawater component from mine drainage.
The sparse distribution of mean values for sul-
phate makes it difficult to interpret the data in
detail. The main distinction appears to be the low
concentrations to the north of the Humber catch-
ment and high concentrations in the central and
southern regions. The high concentrations of sul-
phate in the central and southern catchment may
reflect a large number of potential sources, in-
cluding effluents from the major urban areas,
agricultural fertilizers, geological sources and at-
mospheric deposition. The geology of the Trent
basin is dominated by Triassic Sandstones and
Marls which have abundant gypsum Žcalcium sul-
phate. deposits ŽEdmunds et al., 1982; Jackson
and Lloyd, 1983., providing an important source
of sulphate from weathering. Smith et al. Ž1997.
estimate that atmospheric deposition contributes
approximately 20% of riverine sulphate loads
within the Humber catchment.
5. Summary
This study has demonstrated the importance of
anthropogenic influences on the large-scale regio-
nal water quality of the Humber catchment. These
anthropogenic influences are dominated by ef-
fluent inputs from the major urban centres, which
appear to be strongly linked to elevated concen-
trations of suspended solids, trace metals, boron
and ammonia. Agriculture is a major source of
TON in the lowland agricultural areas. Coal min-
ing, and subsequent abandonment and discharge
of mine waters into the rivers draining the coal-
fields, provides an important source of iron to the

Table 1
Major factors responsible for high concentrations of determinands

Sewage Tidal Agriculture Bedrock Modern Relict Mining Acid rain Type
re-suspension seawater seawater
U U
Suspended solids A

U
Ammonia B
U U
Total oxidized nitrogen E

U U
Calcium ŽU . D
U U
Chloride F
U U U
Magnesium D
U U
Sulphate ? ŽU . ŽU . ? G

U
Aluminium ŽU . A
U U
Boron ? H
U U U
Cadmium C
U U
Chromium A
U U
Copper A
U U U
Iron C
U U U
Lead C
U
Nickel B
U
Zinc ? B
U
Denotes major contributary factor; ŽU . denotes probable contributary factor; ? denotes possible contributary factor.
 T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26
central Humber catchment. Historical ore mining
activity during the Industrial Revolution was re-
sponsible for contaminating sediments and soils
in the upper reaches of certain rivers in Der-
byshire and North Yorkshire. These sediments
continue to provide a major localized source of
cadmium and lead in the upper reaches of these
rural upland rivers.
Determinands whose distribution is not directly
related to anthropogenic activity include calcium
and magnesium, which are subject to geological
controls, particularly the distribution of carbonate
minerals within the bedrock. High concentrations
of chloride, boron, magnesium and calcium in the
Humber estuary result from the ingression of
modern seawater into the estuary and are thus
controlled by tidal effects. High concentrations of
these determinands in South Yorkshire, particu-
larly in the Don catchment, may also originate
from relict seawater from the Carboniferous
strata, discharged via mine drainage. Tidal circu-
lation is responsible for elevated concentrations
of suspended solids and trace metals with a high
particulate component Žcadmium, chromium, cop-
per, iron and lead. within the estuary and tidal
river reaches.
With regard to the sources of the chemical
determinands, eight broad types characterize the
patterns observed ŽTable 1.. These types are as
follows:
䢇 Type A Žsuspended solids, aluminium,
chromium and copper. ᎏ effluent inputs from
urban centres and tidal re-suspension;
䢇 Type B Žammonia, nickel and zinc. ᎏ effluent
inputs from urban centres;
䢇 Type C Žcadmium, iron and lead. ᎏ effluent
inputs from urban centres, tidal re-suspension
and mining;
䢇 Type D Žcalcium and magnesium. ᎏ bedrock,
modern seawater and relict seawater sources;
䢇 Type E Žtotal oxidized nitrogen. ᎏ effluent
inputs from urban centres and agricultural
runoff;
䢇 Type F Žchloride. ᎏ modern and relict seawa-
ter sources;
䢇 Type G Žsulphate. ᎏ effluent inputs from
25
urban centres, bedrock, modern seawater and
relict seawater;
䢇 Type H Žboron. ᎏ effluent inputs from urban
centres and modern seawater.
6. Concluding remarks
A vast database of water quality data have been
brought together under LOIS, using the extensive
datasets collected by the Environment Agency
and the LOIS community. The application of GIS
mapping techniques has facilitated the simplifica-
tion and presentation of a complex and highly
heterogeneous dataset. The maps of the average
concentrations of determinands produced by these
methods are vital for an understanding of the
broad-scale characteristics and controls on water
quality in a major drainage system. The maps
have permitted visual inspection of relationships
between elements from a spatial perspective. The
next step in interpreting this regional water qual-
ity is to examine a broader suite of inter-element
relationships in a graphical environment to inves-
tigate key chemical signatures across the catch-
ment and identify discrete source-type localities,
for more detailed examination of hydrochemical
controls. This work has been taken forward in a
companion paper ŽJarvie et al., 2000.. The
database compiled under LOIS provides a host of
other research possibilities in relation to regional
water quality, particularly when combined with
other large-scale spatial datasets such as land-use
and geology, and with more detailed and special-
ized monitoring and process-focused research
which make up the LOIS Core and Special Topic
programmes.
Acknowledgements
We would like to thank Andrew Eatherall,
David Hill, Dave Morris, Alice Robson, Isabella
Tindall and Paul Wass at Institute of Hydrology
for providing useful information. The visit of
Takashi Oguchi to the Institute of Hydrology for
26 T. Oguchi et al. r The Science of the Total En¨ ironment 251 r 252 (2000) 9᎐26
this research was supported by a grant from Min-
istry of Education, Science, Sports and Culture,
Government of Japan.
References
Allen Dowing, R., Howitt, F., 1969. Saline groundwaters in the
carboniferous rocks of the English East Midlands in rela-
tion to the geology. Q. J. Eng. Geol., 1: 241᎐269.
Bradley, S.B., Cox, J.J., 1986. Heavy metals in the Hamps and
Manifold valleys, North Staffordshire, UK: distribution in
floodplain soils. Sci. Total Environ., 50: 103᎐128.
Burton, J.D., 1976. Basic properties and processes in estuarine
chemistry. In: J.D. Burton, P.S. Liss ŽEds.., Esturine chem-
istry. Academic Press, London, pp. 1᎐36.
Edmunds, W.M., Bath, A.H., Miles, D.L., 1982. Hydrochemi-
cal evolution of the East Midlands Triassic sandstone
aquifer, England. Geochim. Cosmochim. Acta, 46:
2069᎐2081.
Ford, M., Tellum, J.H., 1994. Source, type and extent of
inorganic contamination within the Birmingham aquifer
system, UK. J. Hydrol., 156 Ž1-4.: 101᎐135.
Frost, R.C., 1979. Evaluation of the rate of decrease in the
iron content of water pumped from a flooded shaft mine in
County Durham, England. J. Hydrol., 40 Ž1r2.: 101᎐111.
Jackson, D., Lloyd, J.W., 1983. Groundwater chemistry of the
Birmingham Triassic Sandstone aquifer and its relation to
structure. Q. J. Eng. Geol. Lond., 16: 135᎐142.
Jarvie, H.P., Neal, C., Robson, A.J., 1997a. The geography of
the Humber catchment. Sci. Total Environ., 194r195:
87᎐99.
Jarvie, H.P., Neal, C., Leach, D.V., Ryland, G.P., House,
W.A., Robson, A.J., 1997b. Major ion concentrations and
the inorganic carbon chemistry of the Humber rivers. Sci.
Total Environ., 194r195: 285᎐302.
Jarvie, H.P., Whitton, B., Neal, C., 1998. Nitrogen and phos-
phorus in east coast UK rivers: speciation, sources and
biological significance. Sci. Total Environ., 210r211:
79᎐109.
Jarvie, H.P., Oguchi, T., Neal, C., 2000. Pollution regimes and
variability in river water quality across the Humber catch-
ment: Interrogation and mapping of an extensive and highly
heterogeneous spatial dataset. Sci. Total Environ., 251r252:
27᎐43.
Lewin, J., Macklin, M.G., 1987. Metal mining and floodplain
sedimentation in Britain. In: F. Gardiner ŽEd.., Internatio-
nal geomorphology 1986 Part 1. Wiley, Chichester, pp.
1009᎐1027.
Macklin, M.G., Hudson-Edwards, K.A., Dawson, E.J., 1997.
The significance of pollution from historic metal mining in
the Pennine orefields on river sediments contaminant fluxes
to the North Sea. Sci. Total Environ., 194r195: 391᎐397.
McNeely, R.N., Neimanis, V.P., Dwyer, L., 1979. Water qual-
ity sourcebook: a guide to water quality parameters. Inland
Waters Directorate, Water Quality Branch, Ottawa, Canada
Ž88 pp..
Millward, G.E., Glegg, G.A., Costello, M.J., Wilson, J.G.,
Emblow, C.S., Kelly, K.S., 1995. Fluxes and retention of
trace metals in the Humber Estuary. Estuarine Coastal
Shelf Sci., 44: 97᎐105.
Moore, R.V., 1997. The logical and physical design of the
Land Ocean Interaction Study database. Sci. Total Envi-
ron., 194r195: 137᎐146.
National Rivers Authority, 1996. Environmental assessment of
selected abandoned minewaters. Report of the National
Rivers Authority, Northumbria and Yorkshire Region.
Leeds Ž54 pp..
Neal, C., Smith, C.J., Jeffery, H.A., Jarvie, H.P., Robson, A.J.,
1996. Trace metal concentrations in the major rivers enter-
ing the Humber estuary, NE England. J. Hydrol., 182:
37᎐64.
Neal, C., House, W.A., Leeks, G.J.L., Marker, A.H., 1997a.
UK fluxes to the North Sea, Land Ocean Interaction Study
ŽLOIS.: river basins research, the first 2 years 1993᎐1995.
Sci. Total Environ., 194r195: 1᎐4.
Neal, C., Robson, A.J., Jeffery, H.A. et al., 1997b. Trace
element inter-relationships for the Humber rivers: infer-
ences for hydrological and chemical controls. Sci. Total
Environ., 194r195: 321᎐343.
Neal, C., House, W.A., Whitton, B.A., Leeks, G.J.L., 1998a.
Foreword to special issue: water quality and biology of UK
rivers entering the North Sea: the Land Ocean Interaction
Study ŽLOIS. and associated work. Sci. Total Environ.,
210r211: 1᎐4.
Neal, C., Fox, K.K., Harrow, M., Neal, M., 1998b. Boron in the
major UK rivers entering the North Sea. Sci. Total Envi-
ron., 210r211: 41᎐51.
Neal, C., Jarvie, H.P., Oguchi, T., 1999. Acid available particu-
late trace metals associated with suspended sediments in
the Humber rivers: a regional assessment. Hydrol. Process.,
13: 1117᎐1136.
Robson, A.J., Neal, C., Currie, J.C., Virtue, W.A., Ringrose,
A., 1996. The water quality of the Tweed and its tributaries.
Inst. Hydrol. Report Ser., 128: 1᎐98.
Robson, A.J., Neal, C., 1997a. A summary of regional water
quality for eastern UK rivers. Sci. Total Environ., 194r195:
15᎐37.
Robson, A.J., Neal, C., 1997b. Regional water quality of the
river Tweed. Sci. Total Environ., 194r195: 173᎐192.
Salomons, W., Forstner, U., 1984. Metals in the hydrocycle.
Springer, Berlin Ž349 pp..
Smith, R.I., Cape, J.N., Binnie, J., Murray, T.D., Young, M.,
Fowler, D., 1997. Deposition of atmospheric pollutants to
the LOIS area. Sci. Total Environ., 194r195: 71᎐85.
Tindall, C.I., Moore, R.V., 1997. The Rivers Database and the
overall data management for the Land Ocean Interaction
Study Programme. Sci. Total Environ., 194r195: 129᎐135.
Younger, P.L., 1997. The longevity of minewater pollution: a
basis for decision-making. Sci. Total Environ., 194r195:
457᎐466.