Mine Water and the Environment

https://doi.org/10.1007/s10230-019-00650-0

TECHNICAL ARTICLE

Dilution Processes of Rainfall‑Enhanced Acid Mine Drainage

Discharges from Historic Underground Coal Mines, New Zealand
Carrie Jewiss1   · Dave Craw1 · James Pope2 · Hana Christenson2 · Dave Trumm2

Received: 19 August 2019 / Accepted: 28 December 2019

© Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract
In much of the world, seasonal weather patterns cause a flush of dissolved contaminants from mined areas at the beginning
of wet seasons. However, on parts of New Zealand’s west coast, the annual rainfall exceeds 6000 mm/year, with frequent rain
days regardless of season; in these conditions, chemically rich flushes are short-lived and subsequently diluted. We studied
two historic underground mine sites on the Denniston Plateau. Historic drainages from the Coalbrookdale workings into the
Cascade Mine area discharge between ≈ 100 and ≈ 1000 L/s, depending on rainfall volume and frequency. The frequent rain
on the plateau dilutes the Coalbrookdale discharge waters, increasing its pH and decreasing dissolved AMD constituents.
During short-term high rainfall events, the increased flow causes a flush of stored AMD for less than 10 h, with decreased
pH and increased dissolved concentrations of AMD constituents. In contrast, historic drainage at the Sullivan Mine showed
little response to rainfall and there was virtually no changes in chemistry during or after high rainfall events. While negative
downstream impacts occur at both sites, this study showed that quantification of the variability within a site’s flow regime
is critical in understanding the impact of a mine site’s AMD in high rainfall areas.

Keywords  Geochemistry · Brunner coal measures · Denniston plateau

Introduction This enables a pH increase if the AMD mixes with circum-

Engineered remediation solutions are common features at
modern mine sites and often require high capital investment
and on-going operational costs (Brown et al. 2002; Kefeni
et al. 2017; Lottermoser 2003; Plumlee and Logsdon 1999;
RoyChowdhury et al. 2015). The number and scale of acidic
drainages that are relics of historical mining make wide-
spread treatment financially non-viable for many systems. In
New Zealand, the government typically targets the highest
risk systems, and many legacy sites do not have remediation
plans. Because of this, prioritisation of remediation occurs,
with a focus on sites with a higher downstream impact.
In unremediated AMD systems, dilution with higher pH
waters can occur downstream of discharges (España et al.
2006; Lottermoser 2003; Waters and Webster-Brown 2016).
* Carrie Jewiss
carrie.jewiss@gmail.com
1 strom 2009; Pak et al. 2015; Wolkersdorfer 2008; Younger
Geology Department, University of Otago, P.O. Box 56,
Dunedin, New Zealand
2 tinctly different from the effect of periodic, torrential rain
CRL Energy, P.O. Box 29 415, Christchurch, New Zealand
neutral waters, causing precipitation of secondary miner-
als, with associated removal of trace metals by adsorption
(Alpers et al. 1993, 1994; Nordstrom 2011; Nordstrom et al.
2015; Park et al. 2016; Younger 2000). The pH increase can
occur via multiple methods (Cánovas et al. 2010; Caraballo
et al. 2016; Lee et al. 2001; Shim et al. 2015); in this study,
both mixing with rainwater and uncontaminated stream
water were studied. Background pH values from non-AMD
impacted streams within the Mangatini and Ngakawau catch-
ments on the West Coast often range from 3.5 to 4.5 (Black
et al. 2005).
The West Coast of the South Island of New Zealand
receives abundant year-round rainfall (Fig. 1a), and this set-
ting is therefore potentially suitable for managed dilution of
AMD from the numerous coal mines in the area (Fig. 1b, c).
The annual rainfall commonly exceeds 6000 mm/year, and
storm events can produce rainfall in excess of 10 mm/hr.
Many papers discuss the impact of seasonal rainfall events
in areas with low annual rainfall (Byrne et al. 2013; Nord-
1997; Younger et al. 2002, 2004). These impacts are dis-

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 Mine Water and the Environment

Fig. 1  a Map of South Island of New Zealand, with colours denoting teaus (this study). c Map showing study site on the Denniston Plateau
yearly rainfall, and direction of prevailing winds shown. b Submap and locations of different sampling sites and surrounding catchments,
of the West Coast area above Westport and Cape Foulwind, showing including Cascade Creek and Whareatea River. The Lake Brazil
locations of two dominant plateaus, the Stockton and Denniston Pla- weather station is located at the Escarpment Mine site

year round, such as at the open-cut mine on the Stockton

Plateau (Figs. 1b, 2; Davies et al. 2011a).
This study addresses a gap in knowledge on the impact
of rainfall on AMD discharge in high rainfall areas and pro-
vides a geochemical and hydrological account of the key
features of high-rainfall AMD dilution systems that are
operating naturally on some AMD discharges from historic
underground mines on the Denniston Plateau (Fig. 1b, c).
These discharge sites have negative effects on freshwater
macroinvertebrate numbers and diversity immediately down-
stream (Clapcott et al. 2016). By quantifying the relative
volumes of surface runoff and underground AMD discharges Fig. 2  Comparative graph showing the impact of rainfall on open cast
during and between rainfall events, hydrogeological assess- mines (Stockton, modified from Davies et al. 2011a) and underground
ments used in conjunction with data from similar sites and mines (Cascade 1 and 2, Coalbrookdale discharge and Sullivan Mine)

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Mine Water and the Environment
studies, allowed identification of different flow regimes,
which will aid in prioritising where remediation strategies
will be most effective.
General Setting
Geology, Topography, and Climate
The Denniston and Stockton Plateaus on the west coast of
the South Island of New Zealand host coal deposits within
the Eocene Brunner Coal Measures (BCM) (Flores and
Sykes 1996). The Plateaus are inverted and uplifted basins
that form a coastal mountain range up to 1400  m high,
often capped by eroded remnants of the BCM, which are
commonly 30–100 m thick and contain up to 5 wt% pyrite.
The BCM comprise transgressive sandstone-dominated
sequences, containing carbonaceous mudstones, conglom-
erates, and shales (Titheridge 1992). These coal measures
unconformably overlie a basement of metamorphosed sedi-
mentary rocks of the Greenland Group (Ordovician–Creta-
ceous) and intrusive granites of the Karamea Suite (Creta-
ceous). The coal measures stratigraphically underlie the Late
Eocene, marine-derived, pyrite-bearing Kaiata Mudstone
(Flores and Sykes 1996).
The Denniston and Stockton Plateaus are elevated at
400–1100 m, with deeply incised streams draining steeply
to the nearby Tasman Sea. Prevailing westerly winds take
up moisture from the Tasman Sea, causing large quanti-
ties of precipitation over this area (Fig. 1a, b; Griffiths and
McSaveney 1983; Tomlinson and Sansom 1994). The Den-
niston Plateau is covered with indigenous shrubland and
grasslands, with temperate forest on the lower slopes (Nichol
and Overmars 2008). Rainfall in this environment increases
with elevation, averaging about 6 m at 700 m elevation, and
is weakly seasonal with slightly wetter winter and spring
conditions. Temperatures typically range from − 4 to 30 °C.
Mining and Mine Drainages on the Plateaus
The Denniston Plateau hosts numerous abandoned under-
ground coal mines, including the principal sites of interest
in this study, the Coalbrookdale drainages that discharge at
Cascade Mine and the Sullivan Mine drainages (Fig. 1c).
These legacy underground workings have numerous drain-
age points for AMD at adit entrances (Fig. 1b). The AMD
discharges into two main catchments: at Cascade Mine, the
AMD from the Coalbrookdale workings discharges into Cas-
cade Creek, which flows into the Buller River catchment; the
Sullivan Mine AMD discharges into Rapid Stream before
coalescing into the Whareatea catchment near the coast
(Fig. 1c). A modern open-cut mine also exists at Cascade
Mine, but the historical workings of interest in this study
originate in the historic Coalbrookdale workings, terminat-
ing above the existing open-cut mine and draining from a
series of adits through the recently closed mine site and into
Cascade Creek (Fig. 1c).
At Stockton Plateau, the legacy underground mines are
overprinted by a large modern opencast mine. AMD drains
into the Mangatini Stream (Fig. 1b) and carries high acidity
and elevated concentrations of dissolved metals, irrespective
of the magnitude of most rain events (Fig. 2; Davies et al.
2011a; Waters and Webster-Brown 2016). Geochemical
differences between mine drainages from underground and
open cut mining operations have been studied (McCauley
et al. 2010; Pope et al. 2010a, b); however, they provide only
a snapshot of mine drainage chemistry without considering
short term changes in chemistry with time (Table 1).
Some studies of temporal changes in mine drainage chem-
istry have been completed. For example, many Stockton
AMD discharges increase in pH from < 3 to ≈ 4–5 in major
rain events, when stream flow rates can exceed 50,000 L/s
(Fig. 2; Davies et al. 2011a). Subsequent remediation work
involving engineered acid neutralisation has rehabilitated
Mangatini Stream (Davies et al. 2011b). Trumm et al. (2016,
2017) also observed changes in the chemistry of receiving
streams near the BCM-hosted Bellvue Mine, where rain-
fall-induced maximum discharges from the underground
workings lag peak flow in the streams by about 1 day. In
this study, we characterise the response of the historic Coal-
brookdale AMD discharges at the recently closed Cascade
Mine and in the AMD-impacted Cascade Creek to rainfall
(Fig. 2).
Methods
Sampling Strategy
Over a period of 18 months, sampling was conducted to
characterise and understand the response to rainfall of the
legacy AMD discharges from historic mine workings on
the Denniston Plateau that have not yet been rehabilitated.
Water quality measurements and dataloggers were installed
at selected sites including locations where v-notch weirs
were installed in streams and drains, and in the mixing zone
where AMD discharges into Cascade Creek (Figs. 3a, 4).
At Sullivan Mine, samples were taken at the adit entrance,
halfway down a terrace covered in iron oxy-hydroxide pre-
cipitates, and at the base of this terrace (Table 2; Fig. 3b).
Flow, Rainfall, pH and Specific Conductance
Measurements
The AMD flowed into a series of drainages in which a series
of v-notch weirs were built. TruTrack (Model WT-HR) data
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 Mine Water and the Environment

Table 1  Comparison of principal features of discharge waters from Denniston Plateau historic underground coal mines (this study) and dis-
charges from Stockton Plateau open cut coal mine (Davies et al. 2011a). AMD acid mine drainage, BCM Brunner coal measures (eocene)
Mine type Denniston underground Denniston underground Stockton open cut

Locality Cascade 1 (historic) Sullivan (historic) Mangatini (active in 2010)

Coal type Pyritic BCM Pyritic BCM Pyritic BCM
AMD baseline discharge flow rate 200 L/s 45 L/s 400 L/s
AMD pH 3 at portal 3 at portal 3 at discharge points
AMD dissolved sulphate 100 mg/L 350 mg/L
AMD specific conductance Variable, 200–600 µs/cm
AMD dissolved Fe redox state Fe2+ at portal (up to 10 mg/L) Rapid oxidation to ­Fe3+ at portal Abundant ­Fe3+
Mean ­Fe3+ < 1 mg/L < 1 mg/L 23 mg/L
Precipitates from AMD Downstream (~ 800 m) ferrihydrite,
Schwertmannite at portal, some Localised jarosite, ferrihydrite
Al oxyhydroxide(s) Fe oxyhydroxide precipitation
downstream
Stream dilution of AMD Principal downstream AMD neutrali- Principal downstream AMD neutrali- Important downstream AMD
sation process sation process mitigation process
Response of AMD to rain events 2–10 × discharge increase Negligible 10–1000× discharge increase
AMD pH change after rain events Variable, 3.2–3.6; with visible Nil Variable, 4–6
lag between increased rain and
increased pH, before decreased pH
in high rainfall events

Fig. 3  a Precipitation of iron

oxyhydroxides on mixing of
AMD in Cascade Creek, located
downstream from Cascade/
Coalbrookdale AMD dis-
charge sites. b Discharge and
simultaneous precipitation of
iron oxyhydroxides at Sullivan
Mine Adit, located to the NW of
Cascade Mine on the Denniston
Plateau

loggers were placed in the v-notch weirs, allowing the height
of the AMD to be measured at 15 min intervals. Calibration
of the water height at 0, 10, and 100 cm was completed before
deploying the sondes, and after each data download, in order
to maintain accuracy. Volumes were calculated using Eq. (1).
Q(Flow Rate, L∕s) = 1365 × Height(m)(2.5)
Rainfall data was taken at 10 min intervals from the
Lake Brazil V8 rain station, at the current Escarpment
Mine site (Fig.  1). A YSI 6920—six-series sonde was
deployed in conjunction with the flow tracker; this sonde
was calibrated before being taken into the field. This
allowed the concurrent measurement of pH and specific
(1) conductance (SPC) with flow rate and rainfall, again at
15 min intervals. A calibrated handheld pH probe was
used to measure the pH in situ during sampling. A YSI

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Mine Water and the Environment
Fig. 4  Site map showing sampling sites and their location with respect to adits and the flow of AMD into surrounding Cascade Creek
556 probe was used to measure dissolved oxygen in situ
during sampling.
Water Chemistry Analyses
Water samples for dissolved elemental analysis were
taken from the stream flows using a sterile single-use
25 or 50 mL syringe. Samples were filtered using sterile
Millipore 0.45 μm cellulose acetate cartridge filters into
100 mL polyethylene bottles (acidified to 2% with quartz-
distilled ­HNO3). Issues around the accuracy of measure-
ments of dissolved metals were of interest in areas with
voluminous precipitation, due to the filter size relative to
the nanoparticular size of the precipitates. Due to this,
Al and Fe measurements at Sullivan, in particular, have
potential error attached. These samples were analysed by
inductively coupled plasma mass spectrometry (ICP-MS)
following the APHA-3125 method (APHA 2005) at the
University of Otago. Samples for total metals were acidi-
fied with H
­ NO3 in the field and stored at 4 °C before ICP-
MS analysis, in accordance with method APHA 3030F
(APHA 2005).
The analysis of major ions from all sample sites was
undertaken by RJ Hill Laboratories Ltd. Digestion was
undertaken on all cations using the APHA-3030 method
(2012, modified). Cations (Ca, Mg, K, Na) were meas-
ured using APHA 3125 B (APHA 2012). Chloride was
measured using a filtered sample by ferric thiocyanate
colorimetry, APHA 4500 ­Cl− E (modified from continu-
ous flow analysis, 2012). Sulfate was measured via ion
chromatography using a filtered sample, APHA 4110 B
(APHA 2012). Ferrous iron analysis was performed in the
field with a Hach DR2800 spectrophotometer with pow-
der pillow phenanthroline reactant sachets, according to
HACH method 8146 (Hach 2007).
13


Table 2  Water chemistry data from cascade/coalbrookdale and sullivan mine sites from a series of sampling campaigns over a period of 18 months
Sample site pH pH Diss Al Diss Fe Diss Ni Diss Zn Diss Mg Diss Mn Diss As Diss ­SO4 Diss Ca Diss Na Diss Cl
Field Lab Concentration (g/m3)

13
Detection LIMIT – 0.1 0.01 0.01 0.00003 0.002 0.01 0.0001 0.0001 1.1 0.42 0.42 0.5
Set 1—March 2017
Cascade 1 3.28 3.3 7.1 1.3 0.026 0.15 2 0.16 0.00035 96 7 2.2 3.1
Coalbrookdale 2.74 2.8 33 19 0.089 0.61 2.8 0.36 0.01600 380 12.4 2.6 2.7
Cas Creek UC 6.13 6.4 bd bd bd bd 1.5 bd 0.00094 1.3 9.6 4.8 4.7
Cas Creek Mix 4.57 4.7 2.8 0.44 0.011 0.076 2.5 0.12 0.00014 71 17 5.2 3.5
Set 2—June 2017
Cascade 1 3.17 3.2 6.87 1.30 0.026 0.135 1.78 0.14 0.00039 95 6.1 2.6 3
Cas Creek Mix 4.29 4.9 2.13 0.18 0.009 0.055 2.37 0.11 bd 58 13.7 4.3 3.6
Set 3—July 2017
Cascade 1 – 3.2 7.22 1.39 0.022 0.124 1.45 0.11 0.00042 90 5.1 2.1 2.4
Coalbrookdale – 2.8 22.32 13.08 0.062 0.421 1.82 0.23 0.00939 270 8.8 2.4 2.5
Cas Creek Mix – 4.8 1.95 0.47 0.008 0.052 1.76 0.09 0.00018 47 11.0 3.6 3.2
Set 4—August 2017
Cascade 1 3.2 3.2 8.61 1.33 0.027 0.153 1.55 0.12 0.00041 107 5.6 2.3 3.1
Set 5—October 2017
Cascade 1 3 3.2 8.00 1.39 0.027 0.142 1.61 0.12 0.00042 99 5 2.3 3.5
Coalbrookdale – 2.9 26.89 13.64 0.069 0.441 1.84 0.23 0.00955 230 4.8 2.3 2.4
Cas Creek Mix 4.4 4.5 2.65 0.72 0.011 0.069 1.73 0.10 0.00016 57 11.7 3.8 3.6
Set 6—December 2017
Cascade 1 – 3.2 8.20 1.26 0.028 0.146 2.23 0.16 0.00029 128 8.1 2.3 3.6
Coalbrookdale – 2.8 35.83 14.77 0.079 0.506 2.50 0.32 0.00765 370 10.7 2.5 3.3
Set 7—Feburary 2018
Cascade 1 3 3.2 9.26 1.50 0.026 0.139 1.86 0.14 0.00040 128 5.5 2.5 4.4
Coalbrookdale – 2.9 22.24 10.16 0.055 0.338 1.82 0.21 0.00489 260 7.3 2.2 3.5
Sul main terrace end 2.9 3.0 9.41 16.47a 0.058 0.305 5.51 0.30 0.00363 210a 8.2 3.0 4.5
Set 8—March 2018
Cascade 1 3.2 3.2 6.30 1.19 0.024 0.129 1.71 0.13 0.00040 134 5.4 2.6 3.7
Coalbrookdale – 2.9 22.24 10.16 0.055 0.338 1.82 0.21 0.00489 260 7.3 2.2 3.5
Sul main portal 3.0 3.0 8.18 18.64a 0.060 0.314 5.31 0.30 0.00565 250a 9.2 3.1 3.9
Sul main terrace end 3.0 3.0 8.31 12.38a 0.060 0.311 5.30 0.30 0.00185 230a 8.9 3.1 3.9
Set 9—June 2018
Cascade 1 3.1 3.3 6.96 1.20 0.028 0.149 1.98 0.14 0.00033 140 7.2 2.5 4.1
Coalbrookdale – 2.9 18.58 10.05 0.056 0.357 1.62 0.21 0.00460 310 7.1 2.5 3.2
Sul Main portal 2.86 3 8.55 19.00a 0.061 0.310 5.19 0.27 0.00660 280a 10.3 3.1 4.3
Mine Water and the Environment
 Mine Water and the Environment

Results
Diss Cl

4.3

–
Contrasting Discharge Zones
Diss Na

There is a distinct variation in appearance of the mine

– water discharges at the Cascade and Sullivan sites. At
3

the Cascade Mine, a series of small historic adits release

AMD, which coalesce into two distinctively different
Diss Ca

acidic discharges. Visible iron (hydr-)oxide precipitates

9.9

were not observed at the adit entrances, nor in the drain-

age channels on the mine site. However, where the adit
discharges enter Cascade Creek, the pH increases from 2.8
Diss ­SO4

to 4.9. This results in an orange coating on pebbles in the

280a

366

creekbed (Figs. 1, 3a).

At Sullivan Mine, the primary discharge exits through
0.00349

0.01200

a blockaded adit. The AMD flows through a channel over

Diss As

a terrace of red coloured precipitates, then down a small

streambed into Rapid Stream. Precipitation on the terrace
has resulted in a precipitate bed of ≈ 1.5 m depth covering
Diss Mn

the 3 m width and 20 m length of the channel. Further pre-
0.28

0.50

cipitation is evident within Rapid Stream where Fe cemen-

tation on the pebbles in the stream bed was observed (de
Joux 2003). At Cascade Mine, this precipitation occurred
Diss Mg

on contact with the higher pH waters downstream of the

5.24

adit entrance, compared to immediate precipitation after

discharging from the adit at Sullivan Mine, prior to further
downstream mixing and precipitation.
Diss Zn

0.305

0.700

 Fe and ­SO4 samples may contain nanoparticulate schwertmannite and/or native sulphur

Precipitate Mineralogy
Diss Ni

0.061

0.120

Precipitate minerals comprising two different textures are

present in the mixing zone in Cascade Creek and on the
Concentration (g/m3)

Sullivan precipitate terrace (Fig. 3). At Cascade Creek,

Diss Fe

15.29a

41.58

precipitation forms a thin orange coating on the pebbles

throughout the creekbed (Fig. 3a). In areas where unim-
pacted tributary water enters the creek, a mixing zone
Diss Al

exists where white precipitates are also observed on the

8.60

13.75

stream bed (Fig. 3a). Saturation index modelling and com-

parison to similar discharge zones indicated ferrihydrite
and aluminium hydroxide were the likely mineralogies
Lab

2.9
pH

(Burgos et al. 2012; Davies et al. 2011a; España et al.

2005, 2006). Scanning electron microscopy (SEM) of the
Field

2.83

orange-coated pebbles in Cascade Creek (Figs. 3a, 5a)

2.8
pH

Sullivan data (Trumm et al. 2005)

showed an irregular surface, with substantial desiccation

cracks (Fig. 5a). Iron and aluminium maps indicate that
Sullivan Precipitate terrace

separate mineral phases control these two key components

in the precipitation zone (Fig. 5c, d).
Sul main terrace end
Table 2  (continued)

Within the Fe-rich Cascade Creek mine precipi-

tate, SEM imagery and semiquantitative EDS analy-
Sample site

sis showed the presence of an Al oxyhydroxide phase that

was locally mixed within the nano- and micro-particulate
a

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Fig. 5  a Scanning electron microscopy (SEM) imagery of orange
precipitate coating on pebble from Cascade Creek (Fig. 3a). b SEM
imagery of orange precipitate collected from Sullivan flatbed (fore-
Fe oxyhydroxide and  deposited on some exposed sur-
faces  (Fig.  5a, c–d).  Coarser-grained Al-rich material
occurs as separate platy crystals ≈ 5–20 µm across and
1–2 µm thick, some of which were rectangular to hexago-
nal in shape (Fig. 5a, c). The fine nanoparticulate nature
of the Al oxyhydroxide phase prevented specific miner-
alogical identification by XRD. Saturation index model-
ling (PHREEQC, Parkhurst and Appelo 1999) of associ-
ated water compositions showed that several common Al
oxyhydroxide minerals (alunite, basaluminite, boehmite,
diaspore, and gibbsite) were supersaturated. Basaluminite
(felsőbányaite) is the most common in AMD environments
similar to Cascade Creek (España et al. 2005, 2006; Nord-
strom 1982; Nordstrom and Alpers 1999; Nordstrom et al.
1984).
At the main Sullivan Mine adit portal, the initial pre-
cipitation forms a large mass at the top of the precipitate
terrace (Fig. 3b), which is amorphous. At the micron (SEM)
scale, the structure of this precipitate was different from that
of Cascade (Fig. 5). Sullivan precipitate terrace samples
consisted of tube-like structures, with submicron globular
shapes, covered in long thin needles or spikes (Fig. 5b). This
13
Mine Water and the Environment
ground of Fig.  3b), showing tubular structure of iron precipitate. c
Iron map of SEM image a. d Aluminium map of SEM image a 
is similar to the “hedgehog” morphology of schwertman-
nite (Burgos et al. 2012; Fernandez-Martinez et al. 2010;
Regenspurg and Peiffer 2005). A previous study by de Joux
(2003) found that there was Fe oxyhydroxide cementation of
pebbles less than 100 m from the adit, within Rapid Stream.
Hydrology
There was a positive relationship between increased rain-
fall and flow rates at the Cascade 1 v-notch (Fig. 6a, b).
Over the 18 month period, ≈ 20 high intensity rainfall events
occurred, resulting in increased stream flow (> 400 L/s)
over a period of hours-days. The highest flow rate was seen
between the 24th and 29th of September 2017 (Fig. 6). Dur-
ing this high rainfall event (Fig. 6b), the peak flow rate was
attained ≈ 11 h after the rain event started. After rainfall had
ceased, the flow rate then dropped slowly for 48 h, from a
peak of ≈ 1200 L/s down to a near baseline level of ≈ 200
L/s, before another rain event increased flow again (Fig. 6b).
Adit discharges from Sullivan mine ranged from ≈ 10
to ≈ 80 L/s, with the flow rate mostly remaining constant
at ≈ 45 L/s and no clear relationship to rain events (de Joux
Mine Water and the Environment

Fig. 6  Rainfall versus flow at

site Cascade 1. a Showing over-
all positive relationship between
increased rainfall and flow rate.
b Enlarged view of rainfall and
flow rate during onset of high
rainfall between 24–30/9/2017,
(graph a, high rainfall event).
A visible lag is seen between
rainfall onset and the peak flow

2003; Trumm et al. 2005). Data logging at that site could
not be reliably completed because of precipitation of iron
oxyhydroxides on the logging devices.
Water Chemistry
Adit discharges on Denniston Plateau had low pH and
elevated concentrations of solutes typical of AMD envi-
ronments, relative to drainages on the plateau that were
not impacted by mining. Water discharged from the
Coalbrookdale discharge sites had pH of 2.8–2.9 over
the 15  month monitoring period, and had concentra-
tions of sulfate (230–380 mg/L), Fe (10–19 mg/L), Al
(18.6–35.8  mg/L), Mn, Ni, and Zn above background
levels (Table 2). A tributary of Cascade Creek that has no
mining activity upstream (Cas Creek UC) had pH of 6.4
with 1.3 mg/L of sulfate and concentrations of Al, Fe, Mn,
Ni, and Zn that were below detection.
In Cascade Creek downstream of the Coalbrookdale
confluence, pH varied from 4.5–4.9 and mineral precip-
itates were observed on the stream bed. Metal concen-
trations in the area of Cascade Creek impacted by the
Coalbrookdale drainage were less than in the Coalbrook-
dale drainage, with Fe ranging from 0.2 to 0.7 mg/L and
Al from 1.9 to 2.8 mg/L. Dissolved Fe speciation indi-
cated > 90% was present as F­ e2+ despite the 85% dissolved
oxygen concentration. The difference in the ratio of Fe
to Al at the two locations indicates that in addition to

13

dilution, Fe is precipitating from solution at a greater rate
than Al, as seen in Fig. 5.
Mine discharge at Cascade 1 had pH 3.2–3.3 and ele-
vated metal concentrations relative to non-impacted water.
Metal concentrations at Cascade 1 were less than in the
Coalbrookdale drainage and the sulfate concentration was
90–140 mg/L, less than half of that in the Coalbrookdale
drainage. Monitoring of pH and specific electrical conduct-
ance (SPC) at Cascade 1 over 6 weeks indicated that rain
events cause variation in both the stream flow and solute
chemistry (Fig. 7). Small to moderate rain events cause
increases in pH and decreases in SPC. A large rain event of
294 mm that began on the 25/09/2017 and increased flow
from a baseline 200 to > 1200 L/s. This was coincident with
an initial increase in pH (from 3.3 to 3.6) and drop in SPC
(from approximately 400–200 µS/cm) over a 14 h period.
This was followed by a sharp decrease in pH and increase
in SPC, which lasted for ≈ 10 h before returning to baseline
levels. This was the only occurrence of this pattern in the
6 week monitoring period.
At Sullivan Mine, the low pH (2.9–3) discharge water
had elevated metal concentrations. Water chemistry was
relatively consistent between the adit discharge point and
the base of the precipitate terrace, with the exception of
the 20–35% decrease in Fe concentration. Iron speciation
Fig. 7  pH (a) and specific
conductance (b) measured
concurrently with flow rate at
the Cascade 1 v-notch showing
multiple rainfall events, includ-
ing one high rainfall event
13
Mine Water and the Environment
analyses at both the top and bottom of the precipitate terrace
showed that > 90% of the dissolved iron was ­Fe2+. Water at
Sullivan mine had higher Fe and trace metal concentrations
but lower Al concentrations than the adit discharge from
Coalbrookdale.
Discussion
Iron Oxidation
The iron concentrations in the AMD were different at the
three sites, with the highest concentration at Sullivan mine,
then Coalbrookdale, and the lowest concentrations at Cas-
cade (Table 2). Iron was predominantly present as F ­ e2+ at all
sites, however the presence of ferric iron precipitates shows
a contrast. Iron precipitates as a sulfate-bearing iron oxyhy-
droxide mineral, presumed to be schwertmannite (SEM EDS
identification) at the Sullivan portal, forming the precipitate
terrace (Fig. 3b) with relatively minor precipitation of iron
oxyhydroxide forming downstream after the confluence with
Rapid Stream. In contrast, AMD from the Coalbrookdale
portal contains dissolved ­Fe2+, which persists in solution
downstream until oxidation; ferrihydrite precipitation occurs
during mixing and dilution at the confluence with Cascade
Mine Water and the Environment
Creek (Fig. 3a). This contrast is at least partly related to the
differences in AMD flow rates emanating from the adits;
Sullivan had a low and constant flow rate, whereas Cascade
has relatively high and variable flow rates (Fig. 6).
The different solubilities of schwertmannite and ferri-
hydrite regulate precipitation of these minerals in different
biogeochemical environments (Pope et al. 2005). Ferrihy-
drite typically precipitates at a higher pH than schwertman-
nite, allowing precipitation after mixing with circumneutral
waters, as seen in Cascade Creek, while schwertmannite
typically precipitates at a lower pH, such as at the Sullivan
portal of this study (Yu et al. 1999, 2002). Analyses of Sulli-
van mine discharge indicate a 20–25% decrease in dissolved
iron over the precipitate terrace. It is possible that precipitate
particulates smaller than the 0.45 µm filter pore size may
have been included in the measured dissolved iron concen-
tration. However, the dominance of ferrous iron in the water
samples and the large accumulation of iron precipitate on the
terrace supports an interpretation that the change in solution
chemistry is caused by precipitation of iron as schwertman-
nite on the terrace.
The Influence of Rainfall on Geochemistry
and Hydrology
Flow rate, pH, and SPC varied in response to rainfall; the
magnitude of this variation was governed by the inten-
sity of the rainfall event, with higher flow rates contribut-
ing to greater changes in pH and SPC (Fig. 7). As sulfate
in the Denniston Plateau AMD is an order of magnitude
more concentrated in the AMD than other anions in solu-
tion (Table 2), the measurement of specific conductance
and by association sulfate has been used as proxy for AMD
Fig. 8  Enlarged graph of
a single high rainfall event
from Fig. 6a, showing pH and
specific conductance (SPC) as a
function of flow rate
in this study, allowing comparison to dilution by rainwa-
ter and stream water. This is in line with previous work by
Nordstrom (2008), which has shown a linear trend between
sulfate concentration and SPC in minewater at circum-
neutral pH (ca. 8). The Cascade 1 v-notch measurements
generally showed little variation in pH (3.2–3.3), but the
highest rainfall (Sept. 26th 2017, Fig. 6), caused a distinct
‘acid flush’ after peak flow is reached. This was shown by
a sharp decrease in pH from 3.5 to 3.2 and a sharp increase
in SPC/AMD, from ≈ 200 to ~ 630 µs/cm. This acid flushing
occurred over a period of 10 h (acid flush, Fig. 8).
Dilution Mixing and Rainfall Dilution
Two contrasting dilution processes occurred in the AMD
discharging from the Cascade/Coalbrookdale adits, facilitat-
ing neutralisation and precipitation of secondary minerals.
All of the AMD mixes with, and is diluted by, the higher pH
of Cascade Creek at the stream confluence (Fig. 3a). The
stream mixing results in precipitation of ferrihydrite and Al
oxyhydroxide at the mixing zone (Fig. 5a, c, d), This type of
mixing is common in AMD environments around the world
(Bigham et al. 1996; España et al. 2005; Lee et al. 2002).
In addition to stream mixing, there is periodic dilution
of the AMD by rainwater incursion within the underground
mine system before discharge (Figs. 6, 7). This mixing and
dilution in the underground source causes increase in pH
and decrease in SPC in response to rainfall events (Fig. 7).
There is a time lag of 10–12 h between the increased flux
of rainwater into the system (Fig. 6) and the increase in pH
of the AMD (Fig. 7). This lag is seen most clearly in Fig. 5,
as the pH mirrors the flow rate, which is not instantaneous
13

with the rainfall. Trumm et al. (2016, 2017) found a similar
effect at the Bellvue site located nearby on the West Coast.
Computational modelling of the impact of rainfall dilu-
tion on the pH and SPC of AMD was completed using data
from the AMD at the Cascade Mine, from water samples
collected during this 18-month study, and a typical New
Zealand rainfall sample with pH ranging from 5.7 to 6
(Holden and Clarkson 1986; Jacobson et al. 2003). This
model showed that changes in flow and chemistry on site
could not be explained by rain water dilution (Fig. 9). Spe-
cifically, at high flows, the pH that was measured in the field
was lower than the calculated value from a rainwater dilu-
tion model. In addition the SPC values, were higher in the
field than those calculated model (Fig. 9). This means that
alongside any dilution from rainwater, another factor was
decreasing pH and increasing SPC. The most likely source is
flushing from the adits during higher rainfall events.
A similar study on the neighboring Stockton Plateau
found that AMD on-site was exacerbated, rather than
diluted, by rainfall events. This was associated with exposed
pyrite and a lack of soil cover on the mine surface (Davies
et al. 2011a). At the Stockton Mine, the baseline pH changed
from ≈ 3 to ≈ 4 during typical high discharges. A pH of ≈ 6
was recorded during short periods in rare, extreme flood
events (Davies et al. 2011a). From this, it was ascertained
that the geochemistry of the AMD produced during floods
in the Mangatini Stream reflects rainfall intensity events on
an hourly scale, as opposed to total rainfall volume (Davies
et al. 2011a).
Acid Flushing
From the modelled dilution curve in Fig. 9, the impact of
acid flushing is seen. Apparently, the incoming rainwater
mobilises acidity from storage in pore spaces and fractures
in the surrounding rock mass. The stored AMD is flushed
Fig. 9  Graph showing discon-
tinuity between measured and
calculated pH and SPC, based
on a 1:1 dilution with rainwater
as a response to increased flow
13
Mine Water and the Environment
out of the pore spaces and is mixed with the AMD in the
adit before discharge.
Similar acid flush events occur on a seasonal basis in
many areas around the world with more predictable climates
than New Zealand’s. These flush events typically occur at
the beginning of the rainy season following a season with
lower rainfall and higher heat levels (Wolkersdorfer 2008;
Younger 1997; Younger et al. 2002, 2004). The extra stored
acidity in these areas is enhanced by evaporation, leaving
highly concentrated AMD and soluble sulfate salts and sec-
ondary minerals such as copiapite, epsomite, halotrichite,
melanterite, and rozenite (Alpers et al. 1994; Hammarstrom
et al. 2005; Nordstrom 2009). When the dry period ends, the
first major rainfall event causes a flush of percolating water,
which dissolves the secondary salts and mixes with the con-
centrated AMD (Alpers et al. 1994; Cravotta III 1994). This
flushing process causes a large increase in the metals and a
pH decrease, before discharging a temporary pulse of con-
centrated AMD (Nordstrom 2009).
The flushing events on the Denniston Plateau are more
frequent but smaller and less well defined than those
described elsewhere (above). The frequent but irregular high
rainfall events seen on the Denniston Plateau may limit the
extent to which stored AMD can build up within the rock
mass. Some rain occurred on 306 of the 456 days of this
study. In addition, the damp climate likely limits the evapo-
ration and precipitation of secondary acid-storing minerals
(Hammarstrom et al. 2005).
In comparing the Stockton Plateau to the Denniston
Plateau, one controlling factor in the differences between
these two sites is the difference in mining style. Mining on
the Stockton Plateau is open-cast, compared to the historic
underground mining on the Denniston Plateau. As outlined
above, at Stockton most rainfall results in acid flushing, due
to the interaction of the rainfall runoff with the exposed
pyrite-bearing rock, before mixing in Mangatini Stream
Mine Water and the Environment
(Davies et al. 2011a). During extreme flood events, pH was
measured at excess of > 5, compared to a baseline level of 3
(Davies et al. 2011a). This contrasts with what was seen at
Cascade, with the runoff through underground mining result-
ing in more moderate dilution of pH and SPC during most
rainfall events (Figs. 6, 7). Acid flushing was only visible
during high rainfall events (Fig. 8).
Conclusions
The West Coast of New Zealand presents an ideal setting
for studying the impact of frequent high rainfall on acidic
drainages from historical underground coal mining. On the
Denniston Plateau, the annual rainfall is commonly in excess
of 6000 mm/year, with 66% of the days in this study having
rain, and rain events distributed throughout the year. A site
at Cascade Mine had discharge water flow rates that var-
ied from ≈ 100 to ≈ 1200 L/s, depending on the volume and
frequency of rainfall. These discharging waters had no vis-
ible precipitation of minerals at the adit entrances. However,
upon mixing with the background stream water ≈ 800 m
Fig. 10  Graphical summary of high and low rainfall impacts on AMD discharge and mixing at Cascade and Sullivan sites on the Denniston Pla-
teau
downstream, the resulting increase in pH caused precipi-
tation of ferrihydrite and basaluminite (Fig. 10a, c). The
nearby Sullivan underground mine adit discharges at a more
stable flow rate of ≈ 45 L/s. This site has precipitated schw-
ertmannite below the adit entrance, and further precipitation
downstream in Rapid Stream. Both sites contained > 90%
­Fe2+ at the discharge point from the adits prior to oxidation
to ­Fe3+ causing precipitation (Fig. 10). The frequent rain
on the plateau allows dilution of the Coalbrookdale/Cas-
cade discharge waters, increasing the pH and decreasing the
dissolved AMD constituents. However, during episodes of
short-term heavy rain, the increased flow results in a distinct
acid water flush of stored AMD (Fig. 10a, c), which shows
up as a short-term (< 10 h) decrease in pH, with a parallel
increase in dissolved AMD constituents (Figs. 7, 9c). No
such changes were seen from rainfall events at Sullivan, with
negligible changes in flow rate and pH (Fig. 10b, d).
From this, it is apparent that the dilution of AMD by
rainfall incursion to the Coalbrookdale workings (Cascade
adit) and later downstream increases the pH, but short-term
(< 10 h) acid flushing following extreme rain events can
have temporary negative effects on the receiving stream
13

environments. Currently, AMD impacts are often quanti-
fied from a single round of tests under one flow regime,
which often fails to measure and identify flushing, causing
the magnitude of flush variations and the lag period between
peak rainfall incursion and peak flush to be overlooked. As
outlined in this paper, these are dynamic systems, which
cannot effectively be quantified by a single round of samples.
Because of this, understanding the details of these flush-
ing events is important for planning and prioritising reme-
diation, with unrecognised flow regimes potentially making
some remediation strategies ineffective and introducing the
need for redundancy measures. It is also important to note
that the receiving environments in this study do not remedi-
ate the AMD, and that the streams still contain high metal
concentrations and lowered pH levels that negatively affect
stream ecology (Clapcott et al. 2016). This study shows that
different systems, all within the same coal measures and
similar climatic environment, can behave very differently,
and that understanding the impact of high rainfall on the
output AMD flow rates and pH is an important step in reme-
diation planning.
Acknowledgements  This research was funded by Ministry of Busi-
ness Innovation and Employment to the Centre for Mine Environment
Research (CMER) led by CRL Energy, and scholarships from the Uni-
versity of Otago, and the AusIMM EET NZ. We gratefully acknowl-
edge the support of the West Coast Regional Council for the use of
their YSI 6-series sonde. Access to the mine site and logistical support
was provided by Bathurst Resources Limited. Dave Barr, Gemma Kerr,
Marianne Negrini and Stephen Read ably provided technical assis-
tance. Thanks to Aaron Dutton, Jason Jewiss, Christine McLachlan
and Emma Scanlan for their assistance in the field.
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