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The illicit manufacture of methamphetamine (MAP) produces substantial amounts of hazardous waste that is dumped illegally. This study presents the first environmental evaluation of waste produced from illicit MAP manufacture. Chemical oxygen demand (COD) was measured to assess immediate oxygen depletion effects. A mixture of five waste components (10mg/L/chemical) was found to have a COD (130mg/L) higher than the European Union wastewater discharge regulations (125mg/L). Two environmental partition coefficients, KOW and KOC, were measured for several chemicals identified in MAP waste. Experimental values were input into a computer fugacity model (EPI Suite™) to estimate environmental fate. Experimental log KOW values ranged from -0.98 to 4.91, which were in accordance with computer estimated values. Experimental KOC values ranged from 11 to 72, which were much lower than the default computer values. The experimental fugacity model for discharge to water estimates that waste components will remain in the water compartment for 15 to 37days. Using a combination of laboratory experimentation and computer modelling, the environmental fate of MAP waste products was estimated. While fugacity models using experimental and computational values were very similar, default computer models should not take the place of laboratory experimentation.
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Acute and chronic environmental effects of clandestine
methamphetamine waste
Lisa N. Kates , Charles W. Knapp, Helen E. Keenan
Department of Civil and Environmental Engineering, University of Strathclyde, 75 Montrose Street, Glasgow G1 1XJ, United Kingdom
Methamphetamine waste was assessed to estimate its environmental impact.
Chemical oxygen demand surpassed European Union wastewater discharge regulations.
Partition coefcients K
and K
were measured for input into a fugacity model.
Fugacity model indicates waste components will remain in water for 15 to 37 days.
Sediment compartment is not predicted to contain evidence of methamphetamine waste.
abstractarticle info
Article history:
Received 5 March 2014
Received in revised form 16 June 2014
Accepted 16 June 2014
Available online xxxx
Editor: Adrian Covaci
Environmental modelling
Clandestine laboratories
Methamphetamine waste
EPI Suite
The illicit manufacture of methamphetamine (MAP) produces substantial amounts of hazardous waste that is
dumped illegally. This study presents the rst environmental evaluation of waste produced from illicit MAP
manufacture. Chemical oxygen demand (COD) was measured to assess immediate oxygen depletion effects. A
mixture of ve waste components (10 mg/L/chemical) was found to have a COD (130 mg/L) higher than the
European Union wastewater discharge regulations (125 mg/L). Two environmental partition coefcients, K
and K
, were measured for several chemicals identied in MAP waste. Experimental values were input into a
computer fugacity model (EPI Suite) to estimate environmental fate. Experimental log K
values ranged
from 0.98 to 4.91, which were in accordance with computer estimated values. Experimental K
values ranged
from 11 to 72, which were much lower than the default computer values. The experimental fugacity model for
discharge to water estimates that waste components will remain in the water compartment for 15 to 37 days.
Using a combination of laboratory experimentation and computer modelling, the environmental fate of MAP
waste products was estimated. While fugacity models using experimental and computational values were very
similar, default computer models should not take the place of laboratory experimentation.
© 2014 Elsevier B.V. All rights reserved.
1. Introduction
The study of pharmaceutical products and illicit drugs in the envi-
ronment rose to prominence in the early 2000s (Heberer, 2002;
Jones-Lepp et al., 2004). Researchers discovered that these com-
pounds are ubiquitous in river water, surface water, and wastewater
(Glassmeyer et al., 2005; Huerta-Fontela et al., 2008; Kasprzyk-
Hordern et al., 2009; Zuccato et al., 2008). As the world population
will be found in the aqueous environment. To date, most research
has focused on detection of these contaminants. Research is lacking
on the short-term and long-term effects of these products in the
environment, such as the adverse physiological and toxic effects on
ecosystems and the persistence of drug residues in both water and
Synthetic drugs that are manufactured illicitly, such as amphetamine
type stimulants (ATS), pose an additional risk to the environment from
clandestine drug laboratories. Methamphetamine (MAP) is the most
commonly produced ATS worldwide, typically manufactured in
clandestine laboratories close to the consumer (UNODC, 2012). The
illicit manufacture of MAP produces a large amount of harmful waste
that is often dumped illegally, creating a potential source of pollution.
One kilogramme of MAP produces 5 to 7 kg of waste that includes
many volatile, ammable, and corrosive chemicals, as well as heavy
metals (White, 2004). Common routes of disposal include poured
down indoor plumbing, direct discharge into surface waters, or the
waste being burned and/or buried (US EPA, 2005). However, illicit
drug manufacturers are often not prosecuted for crimes related to
pollutingthe environment due tothe costs associated with prosecution
and lack of research in this area.
Science of the Total Environment 493 (2014) 781788
Corresponding author at: Intrinsik Environmental Sciences Inc., 736 8th Avenue SW,
Suite 1060, Calgary, Alberta T2P 1H4, Canada. Tel.: +1 403 237 0275.
E-mail address: (L.N. Kates).
0048-9697/© 2014 Elsevier B.V. All rights reserved.
Contents lists available at ScienceDirect
Science of the Total Environment
journal homepage:
To aid in the detection and prosecution of an illicit dumpsite, an
understanding of the chemical behaviour of the waste components is
essential. The fate of contaminants entering the environment is depen-
dent on their physicochemical properties, such as hydrophobicity,
vapour pressure, and stability (Walker et al., 1996). The use of partition
coefcients in environmental modelling of organic chemicals is useful in
predicting the behaviour of a contaminant in the environment, con-
taminants such as MAP waste. However, an environmental model is
only as reliable as the information input into the scenario. Therefore,
to generate the most reliable model as possible, it is essential to gain
as much information about the dumpsite and the chemicals as feasible.
Information that will aid the reliability of the model includes the organic
carbon content of the dumpsite and partition coefcients of the waste
Two useful partition coefcients that are readily measureable in the
laboratory are the octanolwater partition coefcient (K
) and the
organic carbon partition coefcient (K
). K
is a measure of the
hydrophobicity of a compound, which is inversely related to polarity.
Generally, as the hydrophobicity of a substance increases, so does its
toxicity. The lipophilicity content that permits compounds to enter
cell membranes is also linked to bioconcentration of organic substances
in aquatic organisms. High K
values are associated with high bio-
concentration factors (BCF).
is often referred to as the organic carbon normalized sorption
constant, which is a measurement of the partitioning behaviour
between water and the organic carbon fraction in a watersediment
system. The K
value factors into account the percentage of organic
carbon present in the sediment, which can greatly inuence the amount
of adsorption.
While K
and K
values provide good information regarding the
fate and long-term consequences of an organic pollutant, short-term
changes may cause just as much if not greater harm. In order to assess
the acute environmental impact of MAP waste, the chemical oxygen de-
mand (COD) can be measured to determine possible oxygen depletion
in receiving waters. COD is an indicative value of water and wastewater
quality that measures the amount of oxygen consumed by organic pol-
lutants through oxidation.
This paper aims to assess initial environmental fate and impact of
organic waste products from clandestineMAP laboratories.This was un-
dertaken using computer modelling in conjunction with laboratory
2. Methods
2.1. Target compounds
The target compounds selected for study were based on waste
products identied in a preliminary proling study (Kates et al.,
2012). In the proling study, organic waste was collected from in-
house MAP synthesis following the Leuckart (Kunalan et al., 2009),
hypophosphorous (Vallely, 1995), or Moscow (Kunalan et al., 2009)
route. Not all of the compounds identied were available to purchase
as analytical standards, which limited the number of compounds avail-
able for this current study. The MAP waste chemicals tested in thisstudy
are summarized in Table 1. All chemicals in this study were purchased
as analytical grade standards from Sigma-Aldrich, UK. Solvents were
HPLC grade and all analyses were completed using high performance
liquid chromatography with a UV detector.
2.2. Chemical oxygen demand, COD
COD was determined using a commercially prepared reactor diges-
tion test tube kit with a range of 01500 mg/L oxygen (Hach-Lange,
UK). Samples were prepared according to the kit instructions and COD
Table 1
General information on MAP waste compounds used in the current study.
Target compound
full name
(CAS number)
Abbreviation Synthetic
λmax (nm) Molecular
MAP Final product C
N149.24 212 COD, K
Benzaldehyde, oxime
NO 121.14 216 COD, K
Benzyl alcohol
BA L, M, H C
O108.14212 K
2,6-DTBP L, M, H C
O206.32 212 K
N-methylace tamide
NO 73.09 COD, K
O 94.11 220 COD, K
P2P L precursor
H by-product
O134.17 208 COD, K
1-P-1,2-P L C
148.16 216 K
LLeuckart; M Moscow; H Hypophosphorous.
782 L.N. Kates et al. / Science of the Total Environment 493 (2014) 781788
values were measured using a portable colorimeter (DR/850 Hach-
Lange, UK). MAP, P2P, N-MA, PHE, and BOX were tested as individual
compounds at concentrationsfrom 1 mg/Lto 100 mg/L. Those ve com-
pounds were also tested as part of a mixture at concentrations from
0.01 mg/L to 100 mg/L/chemical. Thus the nal chemical concentrations
in the mixture solution ranged from 0.05 mg/L to 500 mg/L.
Solutions were made up in Nanopure water (Barnstead Nanopure,
ThermoFisher Scientic, UK). According to the kit manufacturer, the
estimated detection limit of the COD method is 30 mg/L (±16 mg/L).
2.3. Octanolwater partition coefcient, K
(Eq. (1)) values were experimentally determined by reversed
phase high performance liquid chromatography (RPHPLC) following
the Organisation for Economic Co-operation and Development (OECD)
standard method 117 (OECD, 1989). The HPLC used was a Dionex Ulti-
Mate 3000 with a C18 column (Techsphere5ODS, 25 cm × 4.6 mm) and
a variable wavelength detector.
KOW ¼Chemical concentration in octanol½
Chemical concentration in water½
High K
values are associated with high BCFs (Eq. (2)) as most
aquatic organisms will uptake organic pollutants through passive
BCF ¼Chemical concentration in biota½
Chemical concentration in water½
BCF has a linear relationship with K
, as shown in Eq. (3).
logBCF ¼alogKOW þbð3Þ
2.4. Soils
Three different articial soils were prepared for the sorption
experiments to provide a range of organic carbon content and to
reduce matrix interferences from polluted site samples. Garden
humus (B&Q, UK), sand (Portland Builder's sand), and clay (WBB
Minerals, UK) were mixed with silt collected from a stream in
Calderglen Country Park, Glasgow, UK (55°4457.48N, 4° 834.40
The moisture and organic carbon content of each soil was deter-
mined following ASTM Standard Method D2974 07a (ASTM, 2007).
The pH was determined using a 1:1 (w/v) slurry of water and sediment,
which was stirred for 30 min, then left to stand for 1 h before a pH
reading was taken.
The composition and physical properties of each soil are shown in
Table 2. Each soil is classied as sandy loom according to British
Standard BS 3882:2007(British Standards, 2007).
2.5. Sedimentwater partition coefcient, K
values of selected MAP waste impurities were measured
following ASTM standard method E1195 01 (ASTM, 2008). Sorption
of MAP, N-MA, PHE, BOX, P2P, and 2,6-DTBP was measured by
equilibrating them in a mixture of water and sediment at constant
temperature (20 °C ± 1 °C) in the dark. The amount of chemical
added was determined by taking into account its water solubility,
predicted adsorption coefcient, and limit of detection (LOD) of the
HPLC-UV method used to quantify the amount of chemical left in the
aqueous phase (details below; LODs calculated following Miller and
Miller, 2010). Initial estimate of each chemical's adsorption coefcient
was determined using Eq. (4), which predicts K
to within one order
of magnitude (Eq. (3) in ASTM, 2008).
lnKOC ¼lnWs0:01 MP25ðÞþ15:1621ðÞ=1:7288 ð4Þ
water solubility, mg/mL
MP melting point, °C (for liquids at 25 °C, MP = 25)
Sediment to water ratios were calculated to achieve chemical sorp-
tion between 20 and 80%. With a xed aqueous volume of 10 mL, the
sediment to water ratios used were 1:2, 1:3, and 1:5. Using 20 mL
glass universal bottles tted with aluminium foil-lined caps, 1.0 mL of
1.0 mg/mL in water of MAP, N-MA, PHE, BOX, and P2P was added to
the sediment. The volume was brought to 10 mL using Nanopure
water (Barnstead Nanopure, ThermoFisher Scientic, UK), for a nal
concentration of 0.1 mg/mL.
The concentration of 2,6-DTBP was less because of its lower water
solubility. The water solubility of 2,6-DTBP is 2.5mg/L at 25 °C, however
one half of that concentration would not completely dissolve in water at
20 °C. As per the standard method, the solution was made up of 10%
acetonitrile (ACN). 2.0 mL of 1.25 mg/L of 2,6-DTBP was added to the
vials, for a nal concentration of 0.25 mg/L.
The contents of the vials were mixed on a roller shaker for 4 h. Vials
were centrifuged at 4500 rpm for 10 min and the supernatant ltered
using a membrane syringe lter (0.45 μm; Millex MF-Millipore). The l-
trate was added to 2 mL autosampler vials, to which bisphenol A (40 μLof
1.0 mg/mL in methanol) was added as internal standard. While bisphenol
A (BPA) is often found in efuents, it is not related to the compounds of
interest from a clandestine MAP laboratory. By selecting an internal stan-
dard unrelated to the chemicals of interest, cross contamination issues
can be eliminated. The absence of BPA in the articial soils was proven
in blank sample runs. The analytical method used to quantify the K
experiment was HPLC with a UV variable wavelength detector. Thus the
internal standard required a chromophore and an elution time that
would not interfere with the compounds of interest, as well as an elution
time that would not signicantly prolong the run time.
Samples were quantied using HPLC (Dionex UltiMate 3000) with a
C18 column (25 cm × 4.6 mm, Techsphere5ODS) and a variable wave-
length detector. Wavelengths were set according to the λmax in
Table 1. The mobile phase was a gradient of ACN and water as follows:
20% ACN, 80% H
O for 1 min, increasing to 40% ACN/60% H
5 min, and held for 7 min for a total run time of 13 min.
was calculated using Eq. (5).
total quantity of chemical sorbed to solids, μg
Boven-dry weight of solids, g
concentration of chemical in water, μg/mL
Table 2
Composition and physical properties articial soils.
Soil #1 Soil #2 Soil #3
Sand 41.56 58.17 78.85
Silt 5.55 7.29 9.41
Clay 2.79 3.65 4.70
Humus 50.10 30.89 7.04
pH 5.39 5.50 5.77
Moisture content (%, 105 °C) 13.90 8.75 2.11
TOC (%, 440 °C) 7.46 4.37 1.44
783L.N. Kates et al. / Science of the Total Environment 493 (2014) 781788
And where G
is determined from HPLC quantication as follows:
total quantity of chemical in control sample, μg
T total quantity of chemical left in water, μg
2.6. Organic carbon partition coefcient, K
Using the organic carbon content of the three manufactured soils
(Table 2), Eq. (6) gives K
as a function of K
KOC ¼Kd100
%OC ð6Þ
%OC Percent organic carbon of soil/sediment
2.7. Prediction of environmental fate fugacity modelling
A user-friendly and freely available fugacity model can be found in
the United States Environmental Protection Agency's (US EPA) com-
puter modelling program Estimation Programs Interface (EPI) Suite
(US EPA, 2012). EPI Suiteuses a Level III fugacity model, meaning it
assumes that the compartments (air, water, soil, and sediment) are
In the EPI Suitefugacity model, it is possible to alter the emission
scenario. Emission values for each compartment were changed to create
a model that simulates dumping of chemicals directly into a body of
water. Default emission values for each compartment (air, water, and
soil) are 1000 kg/h. The emission values in this work were changed
to: air: 0 kg/h, water: 1000 kg/h, soil: 0 kg/h.
3. Results and discussion
3.1. Acute impact of MAP waste
COD can be used as an evaluative tool on the immediate impact of
chemical waste in the environment. Results of the COD tests on MAP
waste are shown in Tables 3 and 4. The results are dened as amount
(mg) of oxygen consumed per litre of sample.
COD is an indirect measurement of oxygen consumption by organic
and inorganic chemicals in water (US EPA, 2009). The addition of
oxidisable contaminants into water systems can result in the depletion
of dissolved oxygen concentration (Harrison, 2007), which has the
potential to harm aquatic species.
The European Union legislated value for COD levels of chemicals
discharged into the environment is 125 mg/L (Council of European
Union Communities, 1991). For individual waste components
(Table 3), this threshold is reached at concentrations of 50 mg/L or
100 mg/L. For the mixture of the ve chemicals (Table 4), the legis-
lated threshold is also exceeded at a total chemical concentration
of 50 mg/L. Comparing the results from the individual chemicals to
the results of the mixture, the MAP waste components do not display
additive effects. At a chemical concentration of 100 mg/L, the sum-
mation of COD from the individual components (1056 mg/L COD)
is comparable to the COD values of the mixture (1081 mg/L COD).
The difference is more pronounced at lower chemical concentra-
tions: at 50 mg/L the sum of the individual components (701 mg/L
COD) is over ve times higher than the COD results from the mixture
(130 mg/L COD). This result suggests that the mixture is less harmful
than the individual components. With the exception of phenol, these
chemicals have few legitimate uses and are more likely to be found in
the environment as part of a mixture. The mixture is a better indica-
tion of a real-life dumpsite scenario.
While concentrations of MAP waste in the environment have not
been explored through case study, concentrations of 10 to 100 mg/L
are exceedingly low for environmental dumping. On many occasions,
clandestine MAP manufacturers will stock pile waste before disposing
of it. In such circumstances, several tons of waste may be discharged
in one location over a short period of time. The COD results indicate
that such an event has the potential to cause depletion in the amount
of dissolved oxygen to such an extent that it would become harmful
to aquatic organisms. In one case study in Canada, a clandestine drug
laboratory was seized based on the discovery of dead sh in a nearby
stream (Hugel, 2010). While it is probable that several factors likely
contributed to the death of the sh, the COD results from this experi-
ment indicate that oxygen depletion is certainly a potential contributor.
3.2. Chronic effects of MAP waste
3.2.1. K
and BCF
Experimentally determined log K
values of MAP waste are com-
pared with EPI Suitecomputer estimated log K
values in Table 5.
Once the K
values were determined, it was possible to calculate
BCFs based on the experimental K
and computer estimated K
also shown in Table 5.
Generally, small molecules with low K
values are more likely to be
water soluble, whereas larger molecules with high K
values are more
likely to dissolve in lipids and adsorb to solids. High K
values are also
associated with increased bioconcentration, which is linearly related to
, which is essentially a measurement of
polarity, can help to predict distribution and persistence of a compound
Table 3
COD of individual MAP waste chemicals (mg/L COD; n = 2).
50 106 141 190 127 137 701
100 201 252 119 235 249 1056
BDL = below commercial kit detection limit of 30 mg/L.
Table 4
COD of ve MA waste chemicals in a mixture (mg/L COD; n = 2).
Individual [chemical]
Total [chemical]
0.01 0.05 35 ± 35
0.1 0.5 BDL
1 5 BDL
10 50 130 ± 4
100 500 1081 ± 25
BDL = below commercial kit detection limit of 30 mg/L.
Table 5
Experimental Log K
values compare to the EPI Suitecomputer estimates and BCF
values based on experimental or EPI SuiteLog K
Chemical log K
Experimental EPI SuiteExperimental EPI Suite
MAP 2.04 2.07 11.13 11.84
BOX 1.45 1.85 2.28 3.68
BA 1.40 1.10 2.27 1.55
2,6-DTBP 4.91 4.92 626.7 639.0
N-MA 0.98 0.70 0.89 0.90
PHE 1.32 1.46 1.98 2.42
P2P 1.77 1.44 4.99 2.80
1-P-1,2-P 1.71 1.11 5.23 1.95
784 L.N. Kates et al. / Science of the Total Environment 493 (2014) 781788
in the environment. Hydrophilic compounds tend to be dissolved and
distributed throughout surface water; corollary lipophilic compounds
tend to become associated with particulate matter, mostly sediments
(Walker et al., 1996).
Comparison of the experimental values with the EPI Suite
shows little variation. Given the range of K
values and their
reporting on a log scale, the experimental and computer estimated
values are remarkably equivalent. The experimental and predicted
log K
values of 2,6-DTBP were nearly identical, whereas the larg-
est difference in values was for 1-P-1,2-P, with a difference of 0.60.
Even though the log K
values are nearly equivalent over the log
scale, the differences become more apparent when the log function
is removed, which may affect environmental compartment distri-
bution, as investigated in Section 3.4.
The chemicals examined from MAP waste display the following
order of lipophilicity, from the lowest to the highest: N-MA b
PHE bBA bBOX b1-P-1,2-P bP2P bMAP b2,6-DTBP. Using the
linear relationship between K
and BCF (Eq. (3)), the same order
can be applied towards the tendency of these chemicals to bio-
accumulate in aquatic organisms.
The BCF values were estimated using the EPI Suitemodel
(Table 5). As the estimates are dependent on K
values, BCFs were cal-
culated using both the default K
values and the experimental K
values. BAF values are expressed in L/kg wet weight of sh, which en-
ables comparison between different species by normalizing for lipid
content.If the percent lipid of the organism is known,this can be accom-
plished by dividing the wet weight (L/kg) by percent lipid, resulting in a
value with units of L/kg lipid weight.
Two chemicals, 1-P-1,2-P and P2P, exhibited notable increases in
BCF when calculated using the experimental log K
sponds to an increase in the potential uptake of these chemicals in
sh. The BCF of 1-P-1,2-P increased by over threefold, from 1.952 to
6.337, when calculated using the experimental log K
value compared
to the computer estimated log K
value. The uptake of P2P also in-
creased when BCF was calculated based on the experimental log K
compared to the computer estimated log K
, displaying a twofold
increase from 2.803 to 5.908 in BCF values.
MAP itself was predicted to be the second most lipophilic compo-
nent of the MAP waste. IfMAP were to bioaccumulate in the lipid layers
of sh, it would be unlikely to enter into the blood stream of the organ-
ism, meaning MAP would not cross the bloodbrain barrier and would
not have the same physiological effects as an organism that ingested
the drug directly. However, other behavioural or toxic effects may
occur as the pollutant is slowly released into the general circulation.
Ghazilou and Ghazilou (2011) observed that male sh had increased
sexual activity when placed in a breglass aquarium with concentra-
tions of MAP ranging from 0.1 to 1.0 mg/L. Changes were observed
after 2 and 5 days of exposure. However after 7 days of exposure
there was a signicant decrease in sexual activity, suggesting that the
sh grew acclimatisedto their environment andadapted to the dopami-
nergic effects of the drug.
values can be greatly inuenced by pH, as described in
Bangkedphol et al. (2009) and Wells (2006).
3.2.2. Sorption of MAP waste onto sediment
Sediment properties have a great inuence over the behaviour of
chemicals in the environment. The extent of adsorption of a chem-
ical onto sediment is an important factor in determining the ulti-
mate fate of chemicals in the environment. Adsorption is affected
by a number of soil properties, such as organic matter content,
clay content, and pH. The extent of adsorption is also affected by
the physicochemical properties of the compound, such as water sol-
ubility and K
(Drillia et al., 2005). The physical properties of the
articial topsoils used in adsorption experiments are shown in
Table 2.
Of the six target compounds studied in the K
experiment, only
four K
values were able to be determined accurately. For MAP,
matrix interferences prevented the resolution of a peak in the
HPLC chromatogram. The lambda max of MAP was previously de-
termined to be 212 nm, which corresponds to many compounds
present in the soil, such as humic matter. The elution time of MAP
also corresponded to the elution of humic matter despite numerous
program optimization attempts. Using an HPLC equipped with a UV
detector, it was not possible to separate MAP from soil matrix inter-
ferences. The other compound that could not be quantied on the
HPLC was 2,6-DTBP. Due to its low water solubility and high hydro-
phobicity, nal water concentrations were below the limits of
detection. Limits of quantication for the HPLC method are as fol-
lows (calculated as per Miller and Miller, 2010): N-MA = 34 μg/L,
P2P = 5 μg/L, PHE = 5 μg/L, BOX = 4 μg/L.
and K
were calculated using Eqs. (5) and (6),showninTable 6.
The K
value represents the chemical's propensity to adsorb to
organic carbon. The K
is calculated from K
to be independent of
sediment organic carbon content.
The ASTM method makes the assumption that the main factor affect-
ing adsorption for non-polar organic chemicals is the organic carbon
content of the sediment. In this study, the chemicals under investigation
are fairly polar. In this case, other sediment properties may have greater
effect on theadsorption behaviour. Otherfactors include physical forces,
chemical forces, hydrogen bonding, hydrophobic bonding, electrostatic
bonding, coordination reactions, and ligand exchanges (Tan, 1998).
Adsorption of organic chemicals onto sediment surfaces is also in-
uenced by several physicochemical properties of the chemical itself.
Examples of those properties include the chemical nature of the ad-
sorbate, water solubility, dissociation capacity, surface charge density,
and polarity.
3.3. Correlation between log K
and log K
It has long been established that there is a linear relationship be-
tween K
and K
(US EPA, 1996). In an effort to predict K
for chemicals that were not tested, a plot was constructed of log K
versus log K
(Fig. 1). Three lines are present on the plot: one line
from experimentaldata and two lines fromEPI Suiteestimated values.
EPI Suiteuses two different methods of estimating K
. One method
is based on K
values (Eq. (7)), the other based on molecular con-
nectivity index (MCI, Eq. (8)).
logKOC ¼0:8679 logKOW0:0004 ð7Þ
logKOC ¼0:5213 MCI þ0:62 ð8Þ
Looking at the correlation coefcients, the R
value from the ex-
perimental data is closer to one (0.978) than both EPI Suite
values (0.938, 0.840), which indicates a stronger linear correlation.
The poorest correlation between log K
and log K
is from the EPI
Suitemethod that calculates log K
from log K
. According to
the EPI Suitemethodology guide, log K
calculated from log
Table 6
Experimentally determined log K
and K
values for MAP waste components.
Soil 1 0.86 1.65 1.44 1.81
Soil 2 1.07 1.69 1.56 1.88
Soil 3 1.20 1.85 1.61 1.90
Average 1.04 1.73 1.54 1.86
10.96 53.70 34.67 72.44
785L.N. Kates et al. / Science of the Total Environment 493 (2014) 781788
has an R
value of 0.877 (n = 68), and an R
value of 0.967 (n =
69) when calculated using MCI.
Using the equation of the line from the experimental data
(Eq. (9)), it is possible to calculate K
values for MAP, 2,6-DTBP,
1-P-1,2-P, and BA based on experimentally determined K
(Table 7).
y¼3:597x4:325 ð9Þ
3.4. Prediction of environmental fate
3.4.1. EPI SuiteComputer Modelling
Equipped with experimental partition coefcients, K
and K
environmental modelling using a fugacity model was conducted. As
each model is only as reliable as the input data, it is important to have
reliable input parameters.
Three different scenarios were run for each chemical two using the
default K
and K
values, the third using the experimental K
values. The only other parameters altered were the emission
values, as described in Section 2.7.Table 8 displays the compartment
distribution from the fugacity model using K
calculated from the de-
fault K
value. Table 9 displays the compartment distribution using
calculated from MCI, and Table 10 is the compartment distribution
from the fugacity model using experimental K
and K
Since compartment distribution is dependent on the physicochemi-
cal properties of the chemicals, it is interesting to compare the three
different fugacity models using three different sources of K
and K
values. For the model scenario of a simulated discharge into water, the
fugacity model in all three instances indicates that seven of eight
chemicals will overwhelmingly remain in the water compartment
The K
value will play a determining factor in the sedimentwater
partitioning. Looking at the K
values from all three scenarios, the EPI
Suitevalues calculated using K
are within the same order of magni-
tude as the experimental K
values. However, the EPI SuiteK
values from MCI calculations are several orders of magnitude higher
for MAP, BOX, and 2,6-DTBP. This change resulted in a difference in
sedimentwater distribution for MAP and BOX of 3%. For 2,6-DTBP,
there are greater disparities between each scenario in the sediment
water compartments. The distribution in the water compartment
ranged from a high of 98% (Table 10) to a low of 65% (Table 9).
Even with the difference in K
values, all the chemicals from MAP
waste tested in this study will remain predominantly in the water com-
partment. This has implications for environmental sampling, indicating
that water samples should be taken as opposed to sediment samples.
The half-life of each chemical, except 2,6-DTBP, is predicted to be
15 days in the water compartment, with 2,6-DTBP having a half-life of
37.5 days. Given the transient nature of clandestine MAP laboratories,
if a dumpsite is discovered after 15 days, there is a possibility that the
laboratory has already been dismantled.
Under the controlled laboratory conditions, experimental K
values corresponded closely to values calculated using the comput-
er model EPI Suite. In the absence of laboratory experimentation, the
fugacity model that most closely represents experimental results is the
model that uses K
as calculated from K
. However, under environ-
mental conditions, the partitioning behaviour may be different. Factors
that can inuence the K
and K
values are sediment properties,
salinity, temperature and pH, (Bangkedphol et al., 2009).
3.4.2. Model assumptions
EPI Suitehas several assumptions and limitations that must be
taken into account when interpreting the results. The model is designed
to be a screening tool and should not be used if measured values are
available. EPI Suiteuses a Level III Fugacity model which has several
assumptions of its own. The Level III model assumes steady state condi-
tions, but not equilibrium conditions. This means the model assumes
Fig. 1. Correlation between log K
and log K
Table 7
values calculated using experimental K
values in Eq. (9).
Chemical Exp. log K
Calc. log K
MAP 2.04 1.77 58.82
BA 1.40 1.59 39.05
2,6-DTBP 4.91 2.57 369.33
1-P-1,2-P 1.71 1.68 47.62
786 L.N. Kates et al. / Science of the Total Environment 493 (2014) 781788
that chemical concentrations in each compartment will approach zero
over time. The Level III model does not assume that each phase is in
equilibrium, meaning that if a chemical is released into one compart-
ment it can partition into the other compartments. In the Level III
model, a chemical is continuously discharged at a constant rate and
achieves a steady state condition when input and output rates are
equal (CCEMC, 2002; US EPA, 2012).
Chemical losses occur through two methods: reaction and advec-
tion. Reactions include biotic or abiotic degradation of the chemical in
each of the four compartments. Advection is the removal of a chemical
from a compartment through losses other than degradation, such as
bulk media transport via river currents. Advection processes are not
considered for the soil compartment. Additional assumptions of the
Level III model are that there are no direct emissions into the sediment
compartment and it cannot model ionizing or speciating chemicals
(CCEMC, 2002; US EPA, 2012).
There are several parameters that can be changed by the user in EPI
Suitein order to create a chemical and site specic model; however,
there are also numerous parameters that cannot be changed. For exam-
ple, a xed temperature of 25 °C is assumed. That temperature will not
reect many countries mean annual temperatures, nor will it take into
account daytime and seasonal variations.
While a site specic model can be approximated, the limitations in
setting parameters will prevent a truly site specic model from being
designed. This once again reinforces the need for laboratory experimen-
tation, particularly in environments that vary considerably from the
model default values. An additional limitation of the model is that mix-
tures cannot be evaluated. After understanding the assumptions and
limitations of the EPI Suitefugacity model, its advantages are also im-
portant to note. Compared to other environmental models, such as a
mass balance model, the fugacity model is easy to understand and it
does not rely on units, but rather it is based on ratios therefore the
units cancel out. In order to properly use a mass balance model, it is
required to have estimated input concentrations of the chemicals. For
this study, concentrations of MAP waste have never been measured or
studied in a large scale, real-life scenario.
Previous research (Pal et al., 2011), measured the half-life value of
MAP to range from 131 to 502 days, which is in contrast with the EPI
Suiteestimated value in the soil of 30 days. In sediment, EPI Suite
predicts a half-life of 135 days for MAP. The focus of this current study
was MAP waste products, not necessarily MAP itself, in a sediment
water system. The US EPA uses EPI Suiteto evaluate new chemicals,
to help estimate harmfulness and persistence in the absence of experi-
mental data. The EPI Suitemodel calculates halflives based on a com-
bination of accumulated published data on 129 organic chemicals and
correlation with 233 test chemicals using the computer model, devel-
oped by Mackay et al. (1999).
The Pal et al. (2011) study was conducted under ideal laboratory
conditions. In a reallife dumpsite scenario, the chemicals will be ex-
posed to environmental conditions, such as temperature uctuations,
precipitation, and wind. Without conducting a mockdumpsite experi-
ment, it may not be feasible to determine an absolute half-life value.
Additionally, each dumpsite will behave differently depending on the
biological activity, environmental conditions and organic carbon
Computer models cannot replace experimental values, as shown
by the difference in half-life values in this instance. However, in the
absence of the ability to conduct year-long experiments, a computer
model can serve as a screening tool to ag chemicals that are estimated
to be harmful to the environment.
4. Conclusions
By using a combination of laboratory experimentation and computer
modelling, the environmental fate of MAP waste products was estimat-
ed. In the immediate term, the waste is likely to be harmful to aquatic
organisms based on the amount of oxygen consumed through the
oxidation reactions of the compounds. A mixture of the individual
waste components was found to consume more oxygen than the indi-
vidual chemicals. For longer-term implications in a discharge-to-water
scenario, the waste is likely to remain in the water compartment and
has a half-life of 15 to 37.5 days. The partitioning indicates that for
suspected water dumpsites of MAP waste, water samples should be
collected within 2 weeks in order to maximize detection. The analysis
of sediment samples is not predicted to contain evidence of clandestine
MAP waste.
Table 8
EPI Suitefugacity model using K
calculated from default K
13 83 2 79 106 12 33 6506
log K
1.10 1.44 0.70 1.46 2.07 1.11 1.85 4.92
Compartment % t
Air 0 11 0.15 45 0 49 0 10 0.01 3 0 137 0 39 0.02 5
Water 99.7 360 99.2 360 99.8 360 99.5 360 99.4 360 99.7 360 99.6 360 72.7 900
Soil 0.02 720 0.1 720 0.02 720 0.02 720 0.01 720 0.02 720 0.05 720 0.03 1800
Sediment 0.24 3240 0.55 3240 0.2 3240 0.5 3240 0.6 3240 0.23 3240 0.3 3240 27.3 8100
% = Percen t of chemical mass in s pecied compartment; t
Table 9
EPI Suitefugacity model using K
calculated from MCI.
21 93 3 187 893 10 813 9194
log K
1.10 1.44 -0.70 1.46 2.07 1.11 1.85 4.92
Compartment % t
Air 0 11 0.15 45 0 49 0 10 0.01 3 0 137 0.01 39 0.01 5
Water 99.7 360 99.2 360 99.8 360 99.1 360 97 360 99.8 360 97.1 360 65.3 900
Soil 0.02 720 0.1 720 0.02 720 0.03 720 0.01 720 0.02 720 0.07 720 0.03 1800
Sediment 0.27 3240 0.55 3240 0.2 3240 0.9 3240 3.1 3240 0.2 3240 2.87 3240 34.7 8100
% = Percen t of chemical mass in s pecied compartment; t
787L.N. Kates et al. / Science of the Total Environment 493 (2014) 781788
From the experimental measurement of K
and K
, a linear corre-
lation was established. K
can be measured very easily, while K
periments are time consuming and labour intensive. By using the
correlation between the two partition coefcients, K
can be estimated
reliably through the measurement of K
. While fugacity models using
experimental and computational values were very similar, default com-
puter models should not take the place of laboratory experimentation.
The authors would like to thank Karl Bresee for a critical review of
the manuscript and for providing valuable feedback regarding the EPI
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Table 10
EPI Suitefugacity model using experimental K
and K
39.05 53.70 10.96 34.67 58.82 47.62 72.44 369.33
log K
1.40 1.77 0.98 1.32 2.04 1.71 1.45 4.91
Compartment % t
Air 0 11 0.15 45.5 0 49.4 0 10 0.01 3 0 137 0.01 39 0.02 5.23
Water 99.6 360 99.4 360 99.8 360 99.6 360 99.6 360 99.6 360 99.5 360 97.9 900
Soil 0.02 720 0.08 720 0.02 720 0.02 720 0.01 720 0.03 720 0.06 720 0.04 1800
Sediment 0.34 3240 0.4 3240 0.2 3240 0.33 3240 0.42 3240 0.37 3240 0.47 3240 2.01 8100
% = Percen t of chemical mass in s pecied compartment; t
788 L.N. Kates et al. / Science of the Total Environment 493 (2014) 781788
... The predicted BCF for MEA was estimated at 11.13 by Kates et al. (2014) and, according to information provided by USEPA (2021a), ranges between 12.20 and 28.10. Nevertheless, only few concentrations of MEA in the southern hawker nymphs were above the LOQs that suggests its maximal possible BCF to be 0.63 in the nymphs exposed to the environmentally relevant concentration of MEA for six days. ...
... Damselfly nymphs are predators that occupy a relatively high trophic level, which suggests that biomagnification could lead to greater PhAC accumulation in tissues (Heynen et al., 2016). Nevertheless, relatively high solubility of MEA in water (predicted median solubility equal to 11.50 g·L -1 according to USEPA, 2021a) and a low octanol-water partition coefficient log K OW reported for MEA (equal to 2.04 according to Kates et al., 2014) suggest rather a steady-state process than biomagnification. There could also be a relationship between BCF and the water intake rate, which may vary between species or within whole taxonomic groups. ...
... In particular, we focus on amphetamine, methylenedioxymethamphetamine (MDMA), and methamphetamine, which are manufactured using drug precursors and other chemicals (EMCDDA 2015). Methamphetamine, produced in illicit laboratories, is the most commonly produced amphetaminetype stimulant (ATS) worldwide (Kates, Knapp & Keenan 2014;UNODC 2020). Regarding the EU market, it is estimated that the amphetamine, MDMA, and methamphetamine consumed in that region is almost exclusively produced in EU member states (EMCDDA & Europol 2019). ...
... Some of the waste generated in manufacturing synthetic drugs is left behind at the illicit laboratories, disposed in sewage systems and rivers, into the soil, burned, or dumped on the road or in other locations (Irvine & Chin 1991;Kates et al. 2014). Dumping waste into the soil or surface water might damage ecosystems, fauna, and flora, but also residents nearby might be at risk when drinking contaminated water or eating goods from contaminated soil (Boerman et al. 2017;Schoenmakers et al. 2016). ...
Full-text available
The production of illicit drugs contributes to important environmental harms. In the European context, the production of synthetic drugs, particularly MDMA and amphetamine (and more recently methamphetamine), increasingly poses environmental challenges. The production of these substances in Europe is mainly concentrated in the Netherlands and to a lesser extent in Belgium. In this contribution we focus on the Belgian case, particularly in Flanders—the Belgian region where synthetic drug production has been more present. The goals of our analysis are 1) to document the presence of illicit synthetic drug production and dumping of chemical waste material in that region, 2) to explore the media coverage of environmental harms associated with those activities, and 3) to identify the range of reported environmental harms. We draw on data from the Belgian Federal Police and on an analysis of 289 news articles published in selected Flemish newspapers (2013–2020). The findings indicate that although there is an increasing trend in the presence of synthetic drug production and dumping sites in Belgium, the details on the nature and extent of environmental harms are often unknown. Besides difficulties around detecting certain types of dumping events, there are also important blind spots in terms of the monitoring of environmental hazards by law enforcement agencies and how that information is shared among the relevant actors.
... The adsorption of the residues of the micropollutants by GAC followed the second-order kinetics (Fig. S8) with the rate constants of bisphenol A, diclofenac and caffeine of 3.67 × 10 −6 , 7.57 × 10 −6 and 6.06 × 10 −7 Area −1 s −1 , respectively ( Fig. 5 ). The adsorption rate constants followed the order of diclofenac > bisphenol A > caffeine, which was consistent with the order of their log K ow values (calculated using the EPI Suite TM from USEPA) ( Table 1 ) ( Kates et al., 2014 ). The higher log K ow values indicate the higher hydrophobicity of the compounds, which tend to be more adsorbable onto GAC ( Simon et al., 2016 ). ...
This study investigated the removal of three selected micropollutants (i.e., bisphenol A, diclofenac and caffeine) in drinking water using the UV-LED/chlorine advanced oxidation process (AOP) followed by activated carbon adsorption. The degradation of bisphenol A, diclofenac and caffeine was predominantly contributed by chlorination (> 60%), direct UV photolysis (> 80%) and radical oxidation (> 90%), respectively, during the treatment by the UV-LED/chlorine AOP at three tested UV wavelengths (i.e., 265, 285 and 300 nm). The most effective UV wavelengths for the degradation of bisphenol A, diclofenac and caffeine were 265, 285 and 300 nm, respectively. The degradation of all the three micropollutants was enhanced with increasing pH from 6 to 8, though the reasons for the pH dependence were different. The residues of the micropollutants and their degradation (by)products were removed by post-adsorption using granular activated carbon (GAC). Interestingly and more importantly, the adsorption rates of the degradation (by)products were 2–3 times higher than the adsorption rates of the corresponding micropollutants, indicating the formation of more adsorbable (by)products after the AOP pre-treatment. The UV-LED/chlorine AOP followed by GAC adsorption provides a multi-barrier treatment system for enhancing micropollutant removal in potable water. The findings also suggest the merit of the sequential use of UV-LEDs followed by GAC in treating chlorine-containing potable water in small-scale water treatment systems (e.g., point-of-use or point-of-entry water purifiers).
... In the urban rivers in Beijing, our previous study showed that METH was one of the most predominant drugs with detection frequency ranging from 65% to 100% [6]. Although METH was observed at trace concentrations in the natural aquatic ecosystem, it may pose negative effect to both humans and other organisms via long-term exposure [7,8]. ...
In this study, removal of methamphetamine (METH)was investigated by UV activated persulfate (PS), and the influence of key factors was evaluated. Results suggested that METH degradation followed pseudo-first order reaction kinetics. The combination of UV and persulfate (UV/PS)could completely degrade 100 μg/L of METH in 30 min with a PS dosage of 200 μM at pH 7. Both hydroxyl radical ( [rad] OH)and sulfate radical (SO 4⁻[rad] )were confirmed to contribute to the degradation of METH. The bimolecular reaction rate constants of METH with [rad] OH and SO 4⁻[rad] were 7.91 × 10 ⁹ and 3.29 × 10 ⁹ M ⁻¹ s ⁻¹ , respectively. The degradation rate constant of METH was proportional to the PS dosage (0–800 μM)and was high at neutral pH condition. The presence of inorganic anions significantly reduced METH degradation to different degrees, with the inhibitory effect order of Cl ⁻ > NO 3⁻ > HCO 3⁻ . The degradation efficiency of METH was suppressed by the presence of humic acid due to the effect of UV absorption and free radical quenching. The degradation intermediates and products were identified by UPLC-MS/MS and possible transformation pathways were proposed. Results suggested that the combination of UV/PS is a promising treatment technique for the removal of METH in the water environment.
... 5 This is supported by the circumstance that clandestine drug producers often dispose chemicals and waste into the environment or the sewer system in order to get rid of unwanted materials. 1,[6][7][8] Between 2013 and 2016, 591 illegal dump sites were found by the authorities in the Netherlands, and in 2013 the average waste amount of such a site was 800 kg. 8 The clandestine laboratory waste has a negative impact on the environment [7][8][9] and the health of people coming into contact with it. 10 The understanding of the composition of such waste is therefore important to support the investigation of these crimes. ...
Full-text available
Chemical waste from the clandestine production of amphetamine is of forensic and environmental importance due to its illegal nature which often leads to dumping into the environment. In this study 27 aqueous amphetamine waste samples from controlled Leuckart reactions performed in Germany, the Netherlands and Poland were characterised to increase the knowledge about the chemical composition and physicochemical characteristics of such waste. Aqueous waste samples from different reaction steps were analysed to determine characteristic patterns which could be used for classification. Conductivity, pH, density, ionic load and organic compounds were determined using different analytical methods. Conductivity values ranged from 1 to over 200 mS/cm, pH values from 0 to 14 and densities from 1.0 to 1.3 g/cm3 . A capillary electrophoresis method with contactless conductivity detection (CE-C4 D) was developed and validated to quantify chloride, sulphate, formate, ammonium and sodium ions which were the most abundant ions in the investigated waste samples. A SPE sample preparation was used prior to GC/MS analysis to determine the organic compounds. Using the characterisation data of the known samples it was possible to assign 16 seized clandestine waste samples from an amphetamine production to the corresponding synthesis step. The data also allowed to draw conclusions about the synthesis procedure and used chemicals. The presented data and methods could support forensic investigations by showing the probative value of synthesis waste when investigating the illegal production of amphetamine. It can also act as starting point to develop new approaches to tackle the problem of clandestine waste dumping.
... [17,60]. Hazardous chemicals enter the environment and surface waters as contaminants and can be harmful to ecosystem by producing adverse physiological and toxic effects [64,65]. ...
Full-text available
Objective: Methamphetamine abuse remains a significant public health concern since its assent to peak popularity in Iran. Methamphetamine possesses one of the most domestic markets among other drugs of abuse in Kermanshah, Iran. Clandestine methamphetamine laboratories employ different methods and consequently a wide range of chemicals for the illicit production of methamphetamine. Yet there is limited information about active pharmaceutical ingredients in methamphetamine samples seized in Kermanshah, Iran. The current study aimed to identify active pharmaceutical ingredients and manufacturing by-products in methamphetamine samples seized in Kermanshah, Iran. As no organ in the body remains unscathed by methamphetamine and its impurities abuse, the other purpose of the present study was to discuss health effects associated with impure methamphetamine abuse in a brief review. Methods: Analytical study was conducted on 53 methamphetamine samples using gas chromatography/mass spectrometry method. We reviewed the health outcomes of methamphetamine abuse and the evidences supporting pharmacological effects of methamphetamine impurities. Results: Analysed methamphetamine samples contained methamphetamine, amphetamine, ecstasy, phenmetrazine, pseudoephedine, tramadol, benzaldehyde, acetic acid and other chemicals. Information has been discussed for common harmful effects of methamphetamine and its impurities abuse. Conclusion: Illicit methamphetamine crystals contained different chemical impurities originated from manufacturing processes and active pharmaceutical ingredients deliberately added to them. The main prominent synthetic routes for methamphetamine synthesis are Leuckart and Nagai methods in Kermanshah, Iran. In addition to the chemical hazards present in methamphetamine laboratories, there are many hazards posed to anyone involved in direct and indirect contact with these contaminants.
Chlorophenols (CPs) are toxic contaminants that tend to accumulate in textile dyeing sludge and pose a threat to the environment through the disposal process. To comprehensively evaluate CPs in sludge, the characteristics and risks of CPs from five textile dyeing plants (TDPs) were investigated in this study. The total concentration of 19 CPs (Σ19 CPs) varied from 170.90 to 6290.30 ng g⁻¹ dry weight (dw), among which high-chlorine phenols accounted for the greatest proportion. The ecological screening level (ESL) of CPs was used to judge their pollution levels, while the risk quotient (RQ) value and dioxin conversion rate were used to analyze their potential risk. The results indicated that CPs may pose a moderate to high risk to the environment. The Fenton process was used to condition the hazardous sludge, and a higher content of CPs was found after conditioning. A lower rate of CP increase was achieved with a reagent dose of 180 mmol/L, H2O2:Fe²⁺ = 1:1, pH of 3~4 and reaction time of 30 min. In summary, the work helps to address the general knowledge gap in the textile dyeing industry and provides a reference for further research.
The immobilized [email protected]2 photocatalytic thin films were fabricated via electrophoretic deposition method. Affordability, scalability, and high chemical stability are some valuable characteristics making woven stainless steel wire mesh a suitable substrate for fabrication of photocatalyst film. The photocatalytic degradation efficiency of the thin film was investigated by removing hard-degradable methamphetamine under natural solar light. The [email protected]2 photocatalyst with AgCl content of about 5% showed the most photocatalytic degradation efficiency. Using Mott-Schottky plots, the flat band potential of prepared photocatalysts was estimated. The flat band potential showed that the conduction band of [email protected]2 is a better candidate for production of superoxide radicals than TiO2. A film thickness of 1629 nm yields optimal photodegradation efficiency. A series of ten sequential cycles for photodegradation of methamphetamine was conducted using thin film which caused neither significant destruction on photocatalytic substrate nor any considerable reduction in efficiency whatsoever. The [email protected]2 thin film-induced mineralization of methamphetamine was reported to be approximately around 91 percent. The photoelectrochemical performance of TiO2 and [email protected]2 thin film was evaluated by LSV technique under solar light and results show that after incorporation of AgCl, the photocurrent density corresponding to the oxygen evolution reaction significantly increased to 1.8 mA cm⁻² at 1.23 V vs RHE.
Full-text available
In order to evaluate the effects of methamphetamine on sexual behavior of fish, saltwater-acclimatized male sailfin molly Poecilia latipinna L. (Pisces) adults were exposed to 0.1, 0.5, 1 mg/L methamphetamine (MA) concentrations and were observed for alterations in sexual behavior at 2 nd , 5 th or 7 th exposure days. The overall changes displayed by the subjected fish included different acute and chronic responses.
Transport and transformation processes are key for determining how humans and other organisms are exposed to chemicals. These processes are largely controlled by the chemicals’ physical-chemical properties. This new edition of the Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals is a comprehensive series in four volumes that serves as a reference source for environmentally relevant physical-chemical property data of numerous groups of chemical substances. The handbook contains physical-chemical property data from peer-reviewed journals and other valuable sources on over 1200 chemicals of environmental concern. The handbook contains new data on the temperature dependence of selected physical-chemical properties, which allows scientists and engineers to perform better chemical assessments for climatic conditions outside the 20-25-degree range for which property values are generally reported. This second edition of the Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals is an essential reference for university libraries, regulatory agencies, consultants, and industry professionals, particularly those concerned with chemical synthesis, emissions, fate, persistence, long-range transport, bioaccumulation, exposure, and biological effects of chemicals in the environment.
Wastewater-derived contaminants (WWDCs) occur in surface water due to inadequate wastewater treatment and subsequently challenge the capabilities of drinking water treatment. Fundamental chemical properties must be understood to reduce the occurrence of known WWDCs and to better anticipate future chemical contaminants of concern to water supplies. To date, examination of the fundamental properties of WWDCs in surface water appears to be completely lacking or inappropriately applied. In this research, the hydrophobicity-ionogenicity profiles of WWDCs reported to occur in surface water were investigated, concentrating primarily on pharmaceuticals and personal care products (PPCPs), steroids, and hormones. Because most water treatment is conducted between pH 7 and 8 and because D(OW), the pH-dependent n-octanol-water distribution ratio embodies simultaneously the concepts of hydrophobicity and ionogenicity, D(OW) at pH 7 - 8 is presented as an appropriate physicochemical parameter for understanding and regulating water treatment. Although the pH-dependent chemical character of hydrophobicity is not new science, this concept is insufficiently appreciated by scientists, engineers, and practitioners currently engaged in chemical assessment. The extremely hydrophilic character of many WWDCs at pH 7 - 8, indicated by D(OW) (the combination of K(OW) and pK(a)) not by K(OW) of the neutral chemical, is proposed as an indicator of occurrence in surface water.
This study presents the first systematic information on the degradation patterns of clandestine drug laboratory chemicals in soil. The persistence of five compounds - parent drugs (methamphetamine, 3,4-methylenedioxymethamphetamine (MDMA)), precursor (pseudoephedrine), and synthetic by-products N-formylmethylamphetamine and 1-benzyl-3-methylnaphthalene) - were investigated in laboratory scale for 1 year in three different South Australian soils both under non-sterile and sterile conditions. The results of the degradation study indicated that 1-benzyl-3-methylnaphthalene and methamphetamine persist for a long time in soil compared to MDMA and pseudoephedrine; N-formylmethylamphetamine exhibits intermediate persistence. The role of biotic versus abiotic soil processes on the degradation of target compounds was also varied significantly for different soils as well as with the progress in incubation period. The degradation of methamphetamine and 1-benzyl-3-methylnaphthalene can be considered as predominantly biotic as no measureable changes in concentrations were recorded in the sterile soils within a 1 year period. The results of the present work will help forensic and environmental scientists to precisely determine the environmental impact of chemicals associated with clandestine drug manufacturing laboratories.
Tributyltin (TBT) is one of the most toxic anthropogenic compounds introduced into the aquatic environment. It has a relatively high affinity for particulate matter, providing a direct and potentially persistence route of entry into benthic sediments. To understand TBT behavior, computational programs are an exceptionally helpful tool for modeling and prediction. EPISuite program was used for evaluation of the prediction data including fate, persistence and toxicity from the partition coefficient values. Without experimental data, the model is useful for prediction but is essentially a default model. A site specific assessment is possible by measuring the partition coefficients and entering the experimental values obtained into the model. This paper describes the results of a study undertaken to determine the partition coefficients and the effect of various parameters on such partition coefficients. The octanol-water partition coefficient (K(ow)) was determined by the OECD shake-flask method, with the logarithm values obtained ranging from 3.9 to 4.9 depending on salinity. The sediment-water partition coefficient (K(d)) was determined by ASTM method of generating Freundlich adsorption isotherms, the obtained values ranged from 88 to 4909 L kg(-1) depending on sediment properties, salinity, pH, and temperature. The experimental partition coefficient K(ow) and K(oc) (calculated from K(d)) were used as input data into the prediction program to provide accurate values for the natural samples in situ. The experimental prediction showed lower toxicity than the default model, but represent actual toxicity and accumulation at the natural site. Moreover, the environmental fate was significantly different when the experimental values and the default values were compared.
Impurity profiling of seized methamphetamine can provide very useful information in criminal investigations and, specifically, on drug trafficking routes, sources of supply, and relationships between seizures. Particularly important is the identification of "route specific" impurities or those which indicate the synthetic method used for manufacture in illicit laboratories. Previous researchers have suggested impurities which are characteristic of the Leuckart and reductive amination (Al/Hg) methods of preparation. However, to date and importantly, these two synthetic methods have not been compared in a single study utilizing methamphetamine hydrochloride synthesized in-house and, therefore, of known synthetic origin. Using the same starting material, 1-phenyl-2-propanone (P2P), 40 batches of methamphetamine hydrochloride were synthesized by the Leuckart and reductive amination methods (20 batches per method). Both basic and acidic impurities were extracted separately and analyzed by GC/MS. From this controlled study, two route specific impurities for the Leuckart method and one route specific impurity for the reductive amination method are reported. The intra- and inter-batch variation of these route specific impurities was assessed. Also, the variation of the "target impurities" recently recommended for methamphetamine profiling is discussed in relation to their variation within and between production batches synthesized using the Leuckart and reductive amination routes.
Pharmaceuticals and recently also illicit drugs have been recognised as emerging environmental contaminants due to their potential environmental impact: frequent occurrence, persistence and risk to aquatic life and humans. This manuscript is part one of the two-part study aiming to provide a better understanding and application of environmental data not only for environmental aims but also to meet forensic objectives. An attempt to use wastewater data is made in order to verify patterns of the usage of drugs (in particular illicit) in local communities. The average usage of cocaine in South Wales was estimated at 0.9 g day(-1) 1000 people(-1), which equals 1 tonne of this drug used or disposed of to sewage annually in Wales. The calculated usage of amphetamine denoted 2.5 g day(-1) 1000 people(-1) and is suspected to be an overestimate. Because no analysis of enantiomers of amphetamine was undertaken, no distinction between amphetamine's legal and illicit usage could be made.