ARTICLE IN PRESS

Water Research ] (]]]]) ]]]–]]]

Review
Environmental chemistry of phosphonates
Bernd Nowack*
. Swiss Federal Institute of Technology Zurich
Institute of Terrestrial Ecology (ITO), . (ETH), Grabenstrasse 3,
CH-Schlieren 8952, Switzerland
Received 16 August 2002; received in revised form 21 January 2003; accepted 31 January 2003

Abstract

Phosphonates are anthropogenic complexing agents containing one or more C–PO(OH)2 groups. They are used in
numerous technical and industrial applications as chelating agents and scale inhibitors. Phosphonates have properties
that differentiate them from other chelating agents and that greatly affect their environmental behavior. Phosphonates
have a very strong interaction with surfaces, which results in a significant removal in technical and natural systems. Due
to this strong adsorption, little or no remobilization of metals is expected. No biodegradation of phosphonates during
water treatment is observed but photodegradation of the Fe(III)-complexes is rapid. Aminopolyphosphonates are also
rapidly oxidized in the presence of Mn(II) and oxygen and stable breakdown products are formed that have been
detected in wastewater. The lack of information about phosphonates in the environment is linked to analytical
problems of their determination at trace concentrations in natural waters. Further method development is urgently
needed in this area, including speciation of these compounds. With the current knowledge on speciation, we can
conclude that phosphonates are mainly present as Ca and Mg-complexes in natural waters and therefore do not affect
metal speciation or transport.
r 2003 Elsevier Science Ltd. All rights reserved.

Keywords: Phosphonates; Chelating agents; Adsorption; Heavy metals; Degradation; Speciation

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2. Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

3. Analysis of phosphonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1. Analytical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2. Concentrations in the environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

4. Surface reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.1. Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.2. Dissolution of minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.3. Remobilization of metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.4. Precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.5. Inhibition of dissolution and precipitation . . . . . . . . . . . . . . . . . . . . . . . . . 7

*Tel.: +41-1-633-61-60; fax: +41-1-633-11-23.

E-mail address: [email protected] (B. Nowack).

0043-1354/03/$ - see front matter r 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0043-1354(03)00079-4
 ARTICLE IN PRESS
2 B. Nowack / Water Research ] (]]]]) ]]]–]]]

5. Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5.1. Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5.2. Photodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5.3. Chemical degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5.4. Degradation during oxidation processes . . . . . . . . . . . . . . . . . . . . . . . . . . 9

6. Speciation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

7. Behavior during wastewater treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

1. Introduction section biodegradation, photodegradation, chemical

degradation and degradation during oxidation processes
Phosphonic acids, compounds containing the Lewis are discussed. The speciation of phosphonates in the
acid moiety R-CP(O)(OH)2, are characterized by a environment covers the next section, which is followed
stable, covalent carbon to phosphorous bond. The by a discussion of their environmental behavior. This
corresponding anions of the phosphonic acids are called section contains a summary of the data on measured
phosphonates. The most commonly used phosphonates concentrations of phosphonates and their behavior
are structural analogues to the well-known aminopoly- during wastewater treatment.
carboxylates such as ethylenediaminetetra acetate
(EDTA) and nitrilotriacetate (NTA). The environmental
fate of these aminopolycarboxylate chelating agents has 2. Properties
received considerable attention [1–5]. Much less is
known about the fate and behavior of the corresponding Table 1 lists the abbreviations, names and structures
phosphonates in the environment [4,6,7]. The existing of the phosphonates discussed in this review. These
reviews are either several years old and therefore do not compounds are known under many different abbrevia-
cover the newest literature [6] or focus on toxicology and tions that vary between the disciplines and countries and
risk assessment based on the limited data that were have changed with time. Phosphonates are effective
available at that time [7]. What is missing is an overview chelating agents according to the IUPAC definition that
of the chemistry of these compounds which can help us chelation involves coordination of more than one sigma-
to understand and predict the environmental behavior electron pair donor group from the same ligand to the
of these compounds more accurately and that can be the same central atom. Phosphonates are used as chelating
basis for a refined risk assessment. The aim of this agents in many applications, e.g. in pulp, paper and
review is therefore to provide an overview of the current textile industry to complex heavy metals in chlorine-free
knowledge of the environmental chemistry of phospho- bleaching solutions that could inactivate the peroxide. In
nates. It concentrates on polyphosphonates, compounds medicine phosphonates are used to chelate radionuclides
containing more than one phosphonic acid group, and for bone cancer treatments [11].
especially aminopolyphosphonates, compounds contain- A recent IUPAC Technical Report [12] critically
ing several phosphonate and one or more amine groups. evaluates the available experimental data on stability
Glyphosate, a herbicide containing a phosphonate, a constants of proton and metal complexes for phospho-
carboxylate and an amine functional group, is not nic acids. It presents high-quality data as ‘‘recom-
discussed in detail in this review. There is, however, mended’’ or ‘‘provisional’’ constants while for
much information available about the environmental example, all constants for DTPMP have been rejected
chemistry and behavior of this compound [8–10]. due to insufficient purity of the parent compound. This
This review starts with a short description of the report will be of great use for all future speciation
properties of phosphonates and their analysis. Phos- calculations and should be the sole source of stability
phonates have a very strong interaction with surfaces constants when ever possible.
and the section discussing the surface reaction follows: The stability of the metal complexes increases with
adsorption, dissolution of minerals, remobilization of increasing number of phosphonic acid groups. Fig. 1
metals, precipitation of phosphonates and inhibition of shows that the monophosphonate aminomethylpho-
precipitation of minerals are covered. In the degradation sphonic acid (AMPA) has the lowest stability constants
Table 1
Abbreviations, names, and structures of the phosphonates covered in this review

Abbreviation Other abbreviations also in use Name Structure

HEDP HEDPA, HEBP 1-Hydroxyethane(1,1-diylbisphosphonic acid) PO (OH )2

H3 C OH
C

PO (OH )2

B. Nowack / Water Research ] (]]]]) ]]]–]]]

NTMP ATMP, NTP, NTPH, NTPO Nitrilotris(methylenephosphonic acid) (HO) 2OP

ARTICLE IN PRESS
(HO) 2OP N PO(OH) 2

EDTMP EDTP, EDTPH, ENTMP, EDTMPO, EDTMPA 1,2-Diaminoethanetetrakis (methylenephosphonic acid) (HO)2OP

(HO) 2OP N
N PO(OH)2

PO (OH)2

DTPMP DETPMP, DTPPH, DETPMPA, DETPMPO Diethylenetriaminepentakis (methylenephosphonic acid) (HO)2OP PO(OH)2

(HO)2OP N N PO(OH)2
N

PO(OH)2

PBTC PBTCA Phosphonobutane-tricarboxylic acid PO(OH)2

COOH
HOOC C

COOH

3
 ARTICLE IN PRESS
4 B. Nowack / Water Research ] (]]]]) ]]]–]]]

20 1 10-6
3- 5-
H EDTMP ZnHEDTMP
2- 5

15 8 10-7 H EDTMP
6

concentration (M)
log K (M + HL)

EDTMP
6 10-7
10
4-
H EDTMP 4-
4
HEDP 4 10-7 ZnH EDTMP
2
NTMP
5
IDMP
AMPA
2 10-7 3-
HEDTMP
7-
- ZnH EDTMP
H EDTMP 3
0 7
2+ 2+ 2+ 2+ 2+ 2+
Mn Fe Co Ni Cu Zn 0
2 4 6 8 10 12
Fig. 1. Stability constants of 1:1 complexes (M+HL) with
pH
transition metals of AMPA, IDMP, HEDP, NTMP and
EDTMP (Irving–Williams series) with data from [12]. Fig. 2. Speciation of 1 mM EDTMP in the presence of 1 mM Zn.
The diagram has been calculated using the constants from [12].

and EDTMP with 4 phosphonic aid groups the highest.

The log K values of the different transition metal The toxicity of phosphonates to aquatic organisms is
complexes follow the Irving–Williams series Mn2+o- low [6,7,17]. Reported values for 48 h LC50 values for
Fe2+oCo2+oNi2+oCu2+>Zn2+. fish are between 0.1 and 1.1 mM [18,19]. Also the
Fig. 2 shows a speciation diagram for the system Zn- bioconcentration factor for fish is very low [20,21].
EDTMP calculated with the constants from [12] with the Phosphonates are poorly absorbed in the gastro-
speciation program ChemEQL [13]. This calculation intestinal tract and most of the absorbed dose was
shows that in the pH range found in technical rapidly excreted by the kidneys [22]. Human toxicity is
applications and in natural waters a large number of also low which can be seen in the fact that phosphonates
possible complexes with different degree of protonation are used to treat various diseases [14,23].
and charge exist. At pH 6 the species H4EDTMP4
,
ZnH3EDTMP3
, ZnH2EDTMP4
and ZnHEDTMP5

occur at a percentage of more than 5% of total 3. Analysis of phosphonates
EDTMP. Complexation of other metals by other
phosphonates is similar and at each pH value several 3.1. Analytical methods
species coexist.
Phosphonates are not only chelating agents but also The absence of a reliable trace analytical method for
very potent inhibitors of mineral precipitation and phosphonates results in a lack of detailed information
growth. This effect works at concentrations well below about the environmental behavior of phosphonates.
the amount needed to chelate all metals. An important Most of the current methods for phosphonate determi-
industrial use of phosphonates is in cooling waters, nation have detection limits above the expected natural
desalination systems and in oil fields to inhibit scale concentrations or suffer from interferences in natural
formation, e.g. barium sulfate or calcium carbonate samples.
precipitation. Phosphonates are also used in medicine to The standard method for the determination of
treat various bone and calcium metabolism diseases [14]. phosphonates is ion-chromatography followed by post-
In detergents phosphonates are used as a combination of column reaction with Fe(III) and detection of the
chelating agent, scale inhibitor and bleach stabilizer [15]. Fe(III)-complexes at 300–330 nm [24–26]. This method
Phosphonates are highly water-soluble while the has a detection limit of about 2–10 mM. Other methods
phosphonic acids are only sparingly soluble. Phospho- have been developed based on post-column oxidation of
nates are not volatile and poorly soluble in organic the phosphonate to phosphate and detection of phos-
solvents. More detailed data on the physico- phate with the molybdenum blue method [27]. Ion-
chemical properties of the phosphonates can be found chromatography with pulsed amperometric detection of
in reference [7]. amine-containing phosphonates [28], ion-chromatogra-
The consumption of phosphonates was 56,000 tons phy with indirect photometric detection [29] and
worldwide in 1998 [16] and 16,000 tons in Europe in capillary electrophoresis with indirect photometric
1999 [4]. Data about the distribution among the various detection have also been described [30]. These methods
phosphonates are available for Europe and the US [6], all have high detection limits of 1 mM or more and are
for the Netherlands [7] and for Germany [4]. HEDP and therefore not suitable for natural systems.
DTPMP are the most important phosphonates based on A very powerful method is the derivatization of
the used volumes. the phosphonic acid group with diazomethane and
 ARTICLE IN PRESS
B. Nowack / Water Research ] (]]]]) ]]]–]]] 5

separation and detection of the derivatives by HPLC- The oxidative breakdown products of NTMP, IDMP
MS [31]. This method is however, not applicable to and FIDMP, have been detected in two WWTPs
natural waters due to interference by the major cations receiving water from textile industry at concentrations
and anions of the water matrix. The only method with a of 0.08 and 0.015 mM FIDMP and 0.49 and 0.3 mM
low enough detection limit in natural samples is an ion- IDMP in the influent [34].
pair HPLC method with precolumn formation of the The expected concentrations in rivers are maximal
Fe(III)-complexes [32]. The phosphonates can be 0.1 mM and with adsorption/photodegradation
measured with a detection limit of 0.05 mM in natural included about 1–4 nM for NTMP and 25 nM for
waters and wastewaters. The method, however, is not HEDP [6,7]. Locally higher concentrations can be
able to quantify bisphosphonic acids such as HEDP at expected because of intermitted discharge of cooling
low concentrations. This is a major drawback because tower water.
HEDP is one of the most used phosphonates [4,6].
The breakdown products of the Mn(II)-catalyzed
degradation of NTMP [33], iminodimethylenephospho- 4. Surface reactions
nic acid (IDMP) and N-formyl-iminodimethylenephos-
phonic acid (FIDMP), can be detected after derivatization 4.1. Adsorption
of the aldehyde group in FIDMP by 2,4-dinitrophenylhy-
drazine and derivatization of the imine-group in IDMP by Phosphonates adsorb very strongly onto almost all
9-fluorenyl methylchloroformate [34]. A detection limit of mineral surfaces. This behavior distinguishes them from
0.01 mM FIDMP and 0.02 mM IDMP has been achieved. the corresponding aminocarboxylates, which exhibit
Anion-exchange chromatography coupled to ICP-MS much weaker interaction with mineral surfaces, espe-
is able is a very promising method for chelating agent cially near neutral pH [40]. Some of the investigated
analysis [35,36]. The method is also applicable to adsorbents for phosphonates are calcite [41], clays
phosphonates and it has been shown that CuEDTMP [42,43], aluminum oxides [44–46], iron oxides [47–49],
can be determined with a very low detection limit in the zinc oxide [49], hydroxyapatite [50,51] and barite [52].
nanomolar range. For all those compounds very strong adsorption is
Preconcentration of phosphonates from natural water observed in the pH range of natural waters. Natural
samples using different adsorbents has been tested [37]. materials are also very potent adsorbents for phospho-
It was found that the investigated phosphonates HEDP, nates, for example sewage sludge [20,21,39,53,54],
NTMP, and EDTMP differed so much in their chemical sediments [54] and soils [55]. Most of these studies,
behavior that a simultaneous enrichment from natural however, have not considered that metal ions might
samples cannot be achieved. Successful preconcentra- significantly alter the adsorption of a chelating agent
tion of the phosphonates NTMP, EDTMP and DTPMP [56]. However, no influence of Fe(III), Zn, and Cu(II) on
from natural waters or wastewaters was achieved using phosphonate adsorption onto goethite was observed
freshly precipitated CaCO3 [32]. Recoveries at the 1 mM [49]. This was explained by the very strong adsorption of
level were 95–102% for an influent sample of a the uncomplexed phosphonate, which resulted in a
wastewater treatment plant. dissociation of the complex at the surface and separate
adsorption of the metal and the phosphonate onto
3.2. Concentrations in the environment different surface sites. Fig. 3 shows the adsorption of
NTMP and the NTMP complexes with Zn, Cu and
No measurements of phosphonates in natural samples Fe(III). Complete adsorption is observed up to a pH of 8
have been reported and only data for wastewaters are and no influence of the complexed metal on the shape of
available. This is mainly due to the fact that most the adsorption edge can be seen. In the pH range of
analytical methods are not able to quantify phospho- natural waters adsorption is therefore very strong. Other
nates in natural waters at low concentrations. Phospho- phosphonates, e.g. HEDP, EDTMP and DTPMP,
nates have been measured in Swiss wastewater treatment adsorb in a similar manner to NTMP.
plants (WWTP) [38]. The concentrations of NTMP were Ca has a very strong positive effect on phosphonate
between o0.05 and 0.85 mM, of EDTMP between adsorption [49]. In the presence of mM Ca concentra-
o0.05 and 0.15 mM and of DTPMP between o0.05 tions, phosphonates were completely adsorbed up to pH
and 1.7 mM. The highest concentration of DTPMP was of 12. The maximum surface concentration of phospho-
found in a WWTP influenced by textile industry. nates was also greatly enhanced in the presence of Ca.
Effluent samples from all investigated WWTP were with This effect can be explained by the formation of ternary
the exception of one case always below the detection surface-phosphonate-Ca complexes. Precipitation of Ca-
limit. Another WWTP influenced by textile industry phosphonates on the surface can be ruled out [49]. When
contained NTMP concentrations in the influent between evaluating the adsorptive capacity of a surface towards
0.2 and 1.1 mM [39]. phosphonates in a natural system, it is therefore
 ARTICLE IN PRESS
6 B. Nowack / Water Research ] (]]]]) ]]]–]]]

100 1 10-6
NTMP
80 8 10-7 2 mM Ca
1 µM Zn
% adsorbed

Fe(III)NTMP
60 1 µM Cu
6 10-7

40 NTMP 4 10-7
ZnNTMP
CuNTMP
20 Fe(III)NTMP 2 10-7
NTMP/ 1 mM Ca

0 0
4 6 8 10 12 4 4.5 5 5.5 6 6.5 7 7.5 8
pH
pH
Fig. 4. Speciation of 1 mM NTMP in the presence of HFO and
Fig. 3. Adsorption of 10 mM NTMP onto goethite in the
in the absence and presence of 1 mM Zn and Cu and 2 mM Ca
absence and presence of equimolar Zn, Cu, and Fe(III) and
without considering adsorption of the phosphonate. Log K
1 mM Ca. Reprinted with permission from [49]. Copyright
values from [12] and [62].
(1999) American Chemical Society.

necessary to conduct the adsorption experiments under Fe(III)NTMP slightly. Cu which forms the strongest
natural Ca concentrations. complexes with NTMP has the largest influence on
Fe(III)NTMP formation. We can therefore conclude
4.2. Dissolution of minerals that dissolution reactions are able to occur at low pH.
However, the strong adsorption of phosphonates,
Dissolution of a mineral phase by chelating agents can especially at low pH, will limit the formation of
be explained in terms of a ligand exchange process and is dissolved Fe(III)NTMP complexes and therefore no
related to the concentration of surface bound ligands. dissolution will occur at low, environmentally relevant
The ligands weaken the metal–oxygen bonds on the concentrations.
surface and enhance the release of metal ions from the
surface into the adjacent solution [57]. Reactions with 4.3. Remobilization of metals
iron oxides are especially of great importance regarding
the speciation of the ligand in solution due to the very Metals adsorbed onto a mineral surface can be
strong Fe(III)-complexes. Reactions like this have been solubilized by chelating agents. This process has always
observed in subsurface systems and have a pronounced been mentioned as one of the most adverse effects of
influence on the mobility of heavy metals [58,59]. elevated chelating agent concentrations in the environ-
Very little is known about the dissolution of iron ment [63].
oxides by phosphonates. It was observed that HEDP Metal adsorption in the presence of phosphonates has
significantly mobilized Fe from natural sediments but no been studied. There is an increase in Cu adsorption in
information was given about the pH value of the the presence of phosphonates at low pH, which is caused
experiments [60]. No enhanced solubilization of Fe by electrostatic effects [49]. At high pH there is a
from river sediment was observed at pH 3 by 0.01 M mobilization of Cu due to the formation of dissolved
NTMP [61]. Cu-phosphonate complexes. Fig. 5 shows as an example
The concentration of the Fe(III)-complex in the the influence of EDTMP on Cu adsorption onto
presence of an iron oxide phase can be calculated when goethite. Overall, the influence of phosphonates on
the stability constants of the Fe(III)-complexes are metal adsorption in the natural pH range from 4 to 8 is
known. Fig. 4 shows the calculated Fe(III)NTMP weak. We can therefore expect that phosphonates have
concentration in a system with NTMP and hydrous only a slight influence on metal remobilization in natural
ferric oxide (HFO). The speciation has been calculated systems. This was actually found during the study of
with the published stability constants for metal-NTMP metal mobilization from river sediments by the phos-
complexes [12] and the NTMP-Fe(III) stability con- phonate HEDP [60]. The only metal to be remobilized
stants from [62] using the program ChemEQL [13]. The was Fe whereas Zn, Cr, Ni, Cu, Pb and Cd were not
formation of Fe(III)NTMP is important at pH values increased compared to a blank sample and only
below 6 in the absence of other metal ions. At pH above dissolution of iron oxides was observed. Remobilization
7 NTMP is present as uncomplexed ligand. 1 mM Ca of Cu, Cd, and Pb from river sediment was only
and equimolar Zn depress the formation of observed at NTMP concentrations above 0.1 mM [61].
 ARTICLE IN PRESS
B. Nowack / Water Research ] (]]]]) ]]]–]]] 7

100 chemical water treatment additives, known as ‘‘thresh-

old inhibitors’’. Phosphonic acids are among the most
80 potent scale inhibitors next to the polyphosphates. They
% Cu adsorbed

poison the crystal growth at concentrations far below

60 stoichiometric amounts of the reactive cations. Models
for this poisoning include inhibition of nucleation,
40 adsorption onto growth sites, distortion of the crystal
lattice, changes in surface charge and association with
20 Cu alone precursors of crystal formation [74,75].
Cu with NTMP
The morphology of crystals formed in the presence of
0 phosphonates is markedly different from those in the
4 6 8 10 12 absence of phosphonates [76]. Phosphonates limit the
pH size of the growing crystals and produce a lag phase in
Fig. 5. Adsorption of 10 mM Cu onto goethite in the absence which crystal growth is greatly reduced [77]. It was
and presence of 10 mM NTMP. Reprinted with permission from found that the ability of different phosphonates to
[49]. Copyright (1999) American Chemical Society. inhibit crystal growth can be interpreted in terms of the
Langmuir adsorption model with the strongest inhibi-
tory effect from compounds that adsorb most strongly
We can therefore conclude that phosphonates probably [78].
have only a marginal influence on metal mobilization in Due to their inhibitory effect on crystal growth it has
the environment. been argued that phosphonates may have an adverse
effect on phosphate elimination by precipitation with
4.4. Precipitation iron or aluminum salts during wastewater treatment
[79,80]. It was found that the phosphonates had an
In many applications, phosphonates are added to influence on flocculation but it was possible to
waters containing high concentrations of dissolved ions compensate for it by increased addition of flocculating
to prevent the formation of precipitates. However, due agent. The resulting particulate precipitation products
to the insolubility of some metal-phosphonates, the were stabilized by the dispersing action of the phospho-
phosphonates itself can precipitate. This phenomenon nates and not retained in the sand filter. Another study,
often occurs in oil field applications when phosphonates however, found no influence of HEDP on phosphate
are injected into the subsurface and are left to interact elimination [60].
with calcium-containing formation waters [64,65].
The solubility of precipitates of NTMP with divalent
metals increases in the order CaoBaoSroMg [66]. The 5. Degradation
insoluble Ca precipitates of DTPMP [67,68], NTMP
[69], and HEDP [70] and the precipitates of NTMP with 5.1. Biodegradation
Fe(II) [71] and Fe(III) [72] have been investigated in
detail. Insoluble products of HEDP are also formed with Phosphonates are similar to phosphates except that
heavy metals such as Pb and Cd [73]. they have a carbon–phosphorous (C–P) bond in place of
The precipitates are important in oil field applications the carbon–oxygen–phosphorous (C–O–P) linkage. Due
or in technical systems where high phosphonate and to their structural similarity to phosphate esters,
high ion concentration occur simultaneously. In natural phosphonates often act as inhibitors of enzymes due in
waters or wastewaters, the phosphonate or Ca concen- part to the high stability of the C–P bond [81]. In nature
trations are far too low to exert any influence on bacteria play a major role in phosphonate biodegrada-
phosphonate concentrations. The solubility of NTMP in tion. The first phosphonate to be identified to occur
the presence of 1 and 5 mM Ca is always above 200 mM naturally was 2-aminoethylphosphonic acid [82]. It is
[49]. In natural waters precipitation reactions are there- found in plants and many animals, mostly in mem-
fore not important. branes. Phosphonates are quite common among differ-
ent organisms, from prokaryotes to eubacteria and
4.5. Inhibition of dissolution and precipitation fungi, mollusks, insects and others but the biological
role of the natural phosphonates is still poorly under-
Scale formation, e.g. precipitation of calcium carbo- stood [83]. Due to the presence of natural phosphonates
nate or calcium sulfate, is a significant problem in in the environment, bacteria have evolved the ability to
commercial water treatment processes including cooling metabolize phosphonates as nutrient sources. Those
water technology, desalination and oil field applications. bacteria able of cleaving the C–P bond are able to use
This scale formation can be alleviated by the use of phosphonates as a phosphorous source for growth.
 ARTICLE IN PRESS
8 B. Nowack / Water Research ] (]]]]) ]]]–]]]

Aminophosphonates can also be used as sole nitrogen in the environment [91]. Phosphonates have a similar
source by some bacteria [84]. reactivity. In distilled water and in the presence of Ca no
The polyphosphonate chelating agents discussed here photodegradation of HEDP was observed but the
differ greatly from natural phosphonates such as 2- addition of Fe(III) and Cu(II) resulted in rapid photo-
aminoethylphosphonic acid, because they are much degradation [20,92]. The mechanism of Fe(III)EDTMP
larger, carry a high negative charge and are complexed photodegradation [93] is equivalent to the photodegra-
with metals. Biodegradation tests with sludge from dation of Fe(III)EDTA [94]. Fe(III)EDTMP is degraded
municipal sewage treatment plants with HEDP and in a stepwise process from the parent compound through
NTMP showed no indication for any degradation based ethylenediaminetrimethylenephosphonate and ethylene-
on CO2 formation [18,20,21]. An investigation of diaminedimethylenephosphonate to ethylenediaminemo-
HEDP, NTMP, EDTMP and DTPMP in standard nomethylenephosphonate which is stable in the presence
biodegradation tests also failed to identify any biode- of Fe(III) and light. For EDTA the photodegradation of
gradation [53]. It was noted, however, that in some tests the Fe(III)-complexes is the major elimination pathway
due to the high sludge to phosphonate ratio, removal of in natural waters [91]. We can therefore expect that
the test substance from solution observed as loss of photodegradation is also very important for the fate of
DOC was observed. This was attributed to adsorption dissolved phosphonates in surface waters. The photo-
rather than biodegradation because no accompanying degradation products of Fe(III)EDTA are readily
increase in CO2 was observed. biodegradable, but this is not the case for phosphonates
However, bacterial strains capable of degrading [95].
aminopolyphosphonates and HEDP under P-limited
conditions have been isolated from soils, lakes, waste- 5.3. Chemical degradation
water, activated sludge and compost [85]. The phospho-
nate phosphonobutane-tricarboxylic acid (PBTC) was Phosphonates are very stable and breakdown of
also rapidly degraded by microbial enrichment cultures uncomplexed phosphonates requires long timescales
from a variety of ecosystems under conditions of low and severe chemical conditions. At temperatures above
phosphate availability [86]. 200 C free NTMP decomposes to various breakdown
The effects of other more accessible P sources on products [96,97]. These conditions are important for the
phosphonate uptake and degradation are of great fate of the chelating agents in technical systems at
environmental importance. Many environments such elevated temperatures, e.g. in cooling waters of power
as activated sludge, sediments and soils that act as a sink plants, but not for natural waters. One study performed
for phosphonates are not characterized by a lack of P at room temperature within the pH range of 2–10
most of the time. Because phosphonates are utilized reported that over a several month period, EDTMP
almost exclusively as P-source, little biodegradation can hydrolyzed under formation of phosphate, phosphite
be expected under these conditions. It has been and hydroxymethylphosphonate (HMP) [98]. Other
demonstrated, however, that simultaneous phosphate phosphonate-containing breakdown products were pre-
and phosphonate utilization by bacteria can occur [87]. sent but were not identified. No information on the
Adsorption of chelating agents by surfaces has been kinetics or the percentage degraded was given.
shown to decrease the biodegradability. The easily In natural waters chelating agents and therefore the
biodegradable NTA for example is much slower phosphonates always occur in the form of metal
degraded when adsorbed to mineral surfaces [88]. It complexes. Studies on the chemical degradation of
can be expected that phosphonates with their higher phosphonates should therefore always include the
affinity to surfaces are much slower degraded in a presence of metals. Degradation of the amine linkage-
heterogeneous compared to a homogeneous system. containing phosphonates NTMP, EDTMP, and
This was found to be the case for N-phosphonomethyl- DTPMP was negligible in metal-ion free oxygenated
glycine, the phosphonate-containing herbicide glypho- solutions, but Ca, Mg, and Fe(II) brought about
sate [89]. conversion to free phosphate at a rate of approximately
Phosphonates are therefore similar to EDTA [3,90] in 1 percent per day [99]. Although the degradation was
that little or no biodegradation is observed in natural classified as hydrolysis, the conversion rate dropped to
systems but that microorganisms have been isolated negligible levels in the absence of O2, indicating that
from these environments capable of degrading the redox reactions play a role. HEDP, which does not
compound. contain an amine linkage, degrades approximately 20-
times more slowly.
5.2. Photodegradation A loss of NTMP in different natural waters (river
waters, groundwaters) and appearance of the degrada-
Photodegradation of the Fe(III)-complexes is an tion products has been observed [21]. The conversion of
important pathway of aminopolycarboxylate elimination NTMP into iminodimethylenephosphonate (IDMP) and
 ARTICLE IN PRESS
B. Nowack / Water Research ] (]]]]) ]]]–]]] 9

HMP was attributed to abiotic hydrolysis and the occurs in oxygen-free suspension of the Mn(III)
subsequent conversion to aminomethylphosphonate containing mineral manganite (MnOOH) and with
(AMPA) and CO2 to microbial degradation. The MnOOH in the presence of oxygen [100]. EDTMP
authors performed a follow-up study in a medium that and DTPMP are also degraded in the presence of Mn(II)
was free of microorganisms, but contained mM levels of and oxygen, although at a slower rate, but not the
Ca, Mg, K, and Na and trace levels (o1 mM) of Fe(III), amine-free HEDP [33]. Two of the breakdown products
Cu(II), Mn(II), and Zn. Complete conversion of NTMP of NTMP, IDMP and FIDMP, have been detected
to IDMP, HMP and AMPA occurred within 32 h. in WWTP [34]. This indicates that manganese-
Because multiple metal ions were present in these catalyzed oxidation of aminopolyphosphonate is likely
investigations [21,99], it was not possible to identify to be an important degradation mechanism in natural
the catalytic agent. waters.
A systematic study on the influence of metal ions on
phosphonate breakdown has been reported [33]. No 5.4. Degradation during oxidation processes
breakdown of NTMP was observed in metal-free
systems and in the presence of Ca, Mg, Zn, Cu(II) and Phosphonates present in natural waters may be
Fe(III) which disagrees to previous results where subject to oxidation and disinfection processes during
degradation of NTMP was observed in the presence of drinking water treatment. No information on the
Ca or Mg [21]. Very rapid degradation of aminopoly- behavior of phosphonates during chlorination is avail-
phosphonates occurred in the presence of Mn(II) and able. Ozonation of NTMP, EDTMP, and DTPMP
molecular oxygen [33]. The half-life for the reaction of resulted in the rapid disappearance of the parent
NTMP in the presence of equimolar Mn(II) and in compound in less than a minute [101]. 60–70% of the
equilibrium with 0.21 atm O2 was 10 min at pH 6.5. The degraded phosphonate was found as phosphate; AMPA
reaction occurs more slowly under more alkaline or and phosphonoformic acid were also detected. The
acidic conditions. In the absence of oxygen no reaction amine-free HEDP was degraded much more slowly with
took place, indicating that an oxidation step was only 15% degradation after 30 min. The reaction path-
involved. The presence of other cations such as Ca, way of EDTMP during ozonation is equivalent to that
Zn, and Cu(II) can considerably slow down the reaction of EDTA [102]. The herbicide glyphosate was formed
by competing with Mn(II) for NTMP (Fig. 6). Catalytic during ozonation of EDTMP with concentration of up
Mn(II) is regenerated by oxygen in cyclic fashion as the to 10 nM [103]. The environmental fate, behavior and
reaction takes place. The hypothesized pathway is that analysis of both AMPA and glyphosate has received
Mn(II)-phosphonate is oxidized by molecular oxygen to considerable attention [10] and the formation of these
the Mn(III)-phosphonate. In an intramolecular redox- compounds during ozonation of an aminopolypho-
reaction the Mn(III) oxidizes the phosphonic acid and is sphonate may change the risk analysis of these
in turn reduced to Mn(II). compounds considerably.
Formate, orthophosphate, IDMP and FIDMP break-
down products have been identified. Breakdown also
6. Speciation

The speciation of chelating agents in the environment

120 can be calculated based on the known stability constants
of the metal–ligand complexes and the measured total
100 concentrations of metals and chelating agents. This
% of inital NTMP

approach has been used to predict the speciation of

80
EDTMP in Rhine water [6]. The simulated speciation was
60 dominated by CuEDTMP and ZnEDTMP. HEDP was
predicted to be mainly complexed with Ca and NTMP
40 no oxygen
with Cu and Zn [104,105]. But how accurate are such
only Mn(II)
20 Mn(II)/ 0.5 mM Ca calculations? There are several points to consider: In
Mn(II)/ 10 µM Zn speciation calculations it is always assumed that equili-
0 brium has been reached in the system. This is not always
0 100 200 300 400 500 the case. Some metal complexes of aminocarboxy-
time (minutes) lates have very slow exchange kinetics [106]. It has been
Fig. 6. Oxidation of 10 mM NTMP in the presence of 10 mM found for example that Fe(III)EDTA is not in equilibrium
Mn(II) in the presence and absence of dissolved oxygen and with other metals in river water due to slow exchange
competing metal ions at pH 7.0. Reprinted with permission kinetics of Fe(III)EDTA [107]. Almost nothing is
from [33]. Copyright (2000) American Chemical Society. known about the exchange kinetics of metal-phosphonate
 ARTICLE IN PRESS
10 B. Nowack / Water Research ] (]]]]) ]]]–]]]

complexes and therefore all equilibrium calculations have Table 2

to be treated with care. Calculated species distribution of HEDP, NTMP, and DTPMP
Most calculations also do not consider that besides in river water. Conditions: 20 nM phosphonates, 29.4 nM
the chelating agent of interest other chelating agents EDTA, 8.6 nM NTA and natural ligands for Cu, Zn and Ni
and natural ligands are present in the water and com- Ca Mg Zn Cu
pete for available metals. The interaction between
the binding properties of phosphonates and fulvic % of total phosphonate
acids is weak [108] but it has been shown that HEDP
considering the natural ligands for Cu and Zn is critical No other ligands 88 12 0 0.1
for obtaining an accurate speciation of chelating agents With EDTA, NTA, natural 88 12 0 0
[109]. ligands
In the following section a speciation model for three NTMP
phosphonates is developed, based on a river water No other ligands 33 25 11 28
sample from Switzerland with well-known composition With EDTA, NTA, natural 55 42 0 0
ligands
of metals, anthropogenic and natural ligands [110].
DTPMP
These ligands compete with the phosphonates for the No other ligands 0 0 24 76
same metals and have to be included in the speciation With EDTA, NTA, natural 41 21 35 2
calculation. The concentration of the phosphonates in ligands
the calculations was set to 20 nM, comparable to EDTA
at that location.
The speciation was calculated for HEDP and NTMP
with the constants from the IUPAC report [12] and for 7. Behavior during wastewater treatment
DTPMP with the constants from [111]. If only total
metals and the phosphonates are taken into considera- The studies about the behavior of phosphonates
tion, speciation is dominated by Cu for DTPMP, Ca for during wastewater treatment can be divided into two
HEDP, and Ca, Mg, Zn and Cu for NTMP. Including groups: field studies with the addition of elevated
EDTA and NTA does not change the speciation concentrations of phosphonates to the influent of the
significantly; however, as soon as the natural ligands treatment plant and investigations at ambient concen-
for Cu and Zn are considered, the calculated speciation trations.
for NTMP and DTPMP changes drastically. For The elimination of phosphonates during wastewater
NTMP the Cu and Zn complexes disappear totally due treatment was found to be very high, even with high
to the very strong binding of Cu to the natural ligands concentrations of added phosphonates of about 10 mM.
and CaNTMP and MgNTMP are dominant. For Elimination of 9.7 mM HEDP in a field experiment was
DTPMP the Ca and Mg complexes also become very about 60% during the sedimentation and 90–97.5%
important with more than 60% of the DTPMP during the biological step with simultaneous FeCl3
complexed by these metals. CuDTPMP is only a minor precipitation [60]. Lower removal rates of 50–60% were
species under these conditions. For HEDP the alkaline found with the addition of 5–10 mM HEDP and 3–7 mM
earth metals Ca and Mg are the major bound metals NTMP to a WWTP without iron-addition [115]. The
under all conditions. The fraction of other metal behavior of 4.5–12 mM DTPMP was followed through
complexes is never above 0.1%. It can be concluded the different treatment steps [39]. It was found that the
that phosphonates are most probably complexed to DTPMP removal in the biological step was 95%. After
alkaline earth metals in natural waters. This calculation the precipitation step with aluminum sulfate about 97%
shows that considering the natural ligands is crucial for of the added DTPMP had been removed. This
obtaining a reasonable result for phosphonate speciation investigation has shown that even without simultaneous
(Table 2). addition of iron or aluminum salts, very good removal
Analytical methods have been developed to determine in the biological step can be achieved.
directly the speciation of aminocarboxylate chelating The second group of studies investigated the fate of
agents [112–114]. In principle these methods should also phosphonates that are already present in the influent of
be applicable to phosphonates. A recent very promising the WWTP. For a 13-day field study a total amount of
method uses anion-exchange chromatography coupled 117 mol of DTPMP was found in the influent of the
to ICP-MS for the separation of metal-chelating agent WWTP compared to an effluent load of 17 mol, meaning
complexes [35,36]. The method is also applicable to that the removal efficiency was 85% [38].
phosphonates and it has been shown that the Elimination of NTMP and EDTMP from another
CuEDTMP complex can be determined. The use of WWTP was at least 80% and 70%, respectively [38].
these methods to determine the speciation of phospho- Because the concentration in the effluent was below the
nates in natural waters is needed. detection limit, this removal efficiency is the lower limit.
 ARTICLE IN PRESS
B. Nowack / Water Research ] (]]]]) ]]]–]]] 11

The fate of NTMP was followed in another WWTP [3] Bucheli-Witschel M, Egli T. Environmental fate and
receiving wastewater from textile industry [39]. The load microbial degradation of aminopolycarboxylic acids.
of NTMP in the influent was 324 mol during the 2-week FEMS Microbiol Rew 2001;25:69–106.
period. No NTMP was detected in the effluent. Taking [4] Knepper TP, Weil H. Study on the entry of synthetic
the detection limit of 0.05 mM as the upper limit of chelating agents and compounds exhibiting complexing
properties into the aquatic environment. Vom Wasser
NTMP concentration the maximal effluent load for the
2001;97:193–232.
2-week period can be calculated to be 23 mol. The [5] Nowack B. Environmental chemistry of aminopolycar-
removal efficiency of the WWTP was therefore at least boxylate chelating agents. Environ Sci Technol 2002;36:
93%. Also the two breakdown products of NTMP, 4009–16.
IDMP and FIDMP, were present at much higher [6] Gledhill WE, Feijtel TCJ. Environmental properties and
concentrations in the influent than in the effluent [34], safety assessment of organic phosphonates used for
with a removal of 87% FIDMP and 96% IDMP. detergent and water treatment applications. In: Hutzinger
The results from field studies and field measurements O, editor. The handbook of environmental chemistry,
have shown that phosphonates are removed very vol. 3, Part F. Berlin, Heidelberg: Springer, 1992,
efficiently in most WWTP and pose only little risk to pp. 261–85.
the receiving waters. [7] Jaworska J, van Genderen-takken H, Hanstveit A, van de
Plasche E, Feijtel T. Environmental risk assessment of
phosphonates, used in domestic laundry and cleaning
agents in the Netherlands. Chemosphere 2002;47:655–65.
8. Conclusions [8] Atkinson D. Toxicological properties of glyphosate—a
summary. In: Atkinson D, editor. The herbicide glypho-
* The very strong adsorption of phosphonates results sate. London: Butterworths, 1985. p. 127–33.
in low dissolved concentrations. [9] Franz JE, Mao MK, Sikorski JA. Glyphosate: a unique
* Little or no remobilization of metals by phospho- global herbicide. ACS Monogr 1997;189:653.
nates is expected. [10] Stalikas CD, Konidari CN. Analytical methods to
* No biodegradation of phosphonate-chelating agents determine phosphonic and amino acid group-containing
is observed in the environment. pesticides. J Chromatogr A 2001;907:1–19.
[11] de Klerk JMH, van Dijk A, van het Schip AD,
* The Fe(III)-complexes are rapidly photodegraded.
Zonnenberg BA, van Rijk PP. Pharmacokinetics of
* Rapid degradation of aminopolyphosphonates oc- rhenium-186 after administration of rhenium-186-HEDP
curs in the presence of Mn(II). to patients with bone metastases. J Nucl Med 1992;33:
* An analytical method for trace measurements in 646–51.
natural waters is urgently needed. [12] Popov K, Ronkk . . aki H, Lajunen LHJ. Critical
om.
* No analytical information on speciation of phospho- evaluation of stability constants of phosphonic acids.
nates in the environment is available. Pure Appl Chem 2001;73:1641–77.
.
[13] Muller B. ChemEQL, 2.0 A program to calculate
chemical speciation, equilibria, titrations, dissolution,
precipitation, adsorption, simple kinetics, px-py dia-
Acknowledgements grams. EAWAG/ ETH, 1996.
[14] Fleisch H. Bisphosphonates: a new class of drugs in
The author is indebted to Jean-Claude Bollinger and diseases of bone and calcium metabolism. Recent Results
V!eronique Deluchat for their fruitful comments to Cancer Res 1989;116:1–28.
earlier versions of this manuscript and to Susan Tandy [15] May HB, Nijs H, Godecharles V. Phosphonates. Multi-
for editing the English. This review was prepared functional ingredients for laundry detergents. Household
in part during a stay at the University of Limoges, Pers Prod Ind 1986;23:50–4.
France. The support of the Reinhold-Beitlich-Founda- [16] Davenport B, DeBoo A, Dubois F, Kishi A. CEH report:
.
tion, Tubingen, Germany, is greatly acknowledged. chelating agents. SRI Consulting, Menlo Park, CA, USA,
2000.
[17] van Hullebusch E, Chazal PM, Deluchat V. Influence of
phosphonic acids and EDTA on bacterial copper
References toxocity. Toxicol Environ Chem 2002;82:75–91.
[18] Huber L. Investigations about the biological degradabil-
[1] Means JL, Alexander CA. The environmental biogeo- ity and fish toxicity of 2 organic chelating agents on
chemistry of chelating agents and recommendations for phosphonic acid basis (ATMP and HEDP). Tenside
the disposal of chelated radioactive wastes. Nucl Chem Deterg 1975;12:316–22.
Waste Manage 1981;2:183–96. .
[19] Schoberl PH. Ecologically relevant data of non-tenside
[2] Wolf K, Gilbert PA. EDTA—Ethylenediaminetetraacetic components in washing and cleaning agents. Tenside
acid. In: Hutzinger O (Ed.), The Handbook of Environ- Surfactants Deterg 1988;25:99–107.
mental Chemistry, vol. 3, Part F. Berlin, Heidelberg: [20] Steber J, Wierich P. Properties of hydroxyethane diphos-
Springer, 1992. p. 243–59. phonate affecting its environmental fate: degradability,
 ARTICLE IN PRESS
12 B. Nowack / Water Research ] (]]]]) ]]]–]]]

sludge adsorption, mobility in soils, and bioconcentra- [37] Frigge E, Jackwerth E. Preconcentration and determina-
tion. Chemosphere 1986;15:929–45. tion of organophosphonic acids: application to natural
[21] Steber J, Wierich P. Properties of aminotris(methylene- waters. Anal Chim Acta 1991;254:63–73.
phosphonate) affecting its environmental fate: degrad- [38] Nowack B. Behavior of phosphonates in wastewater
ability, sludge adsorption, mobility in soils, and treatment plants of Switzerland. Water Res 1998;32:
bioconcentration. Chemosphere 1987;16:1323–37. 1271–9.
[22] Calvin G, Long PH, Stitzel KA, Anderson RL, Balmbra [39] Nowack B. Aminopolyphosphonate removal during
RR, Bruce RD, Bhatt A, Miller PM, Broadmeadow A. wastewater treatment. Water Res 2002;36:4636–42.
Ethyelenediaminetetra(methylenephosphonic acid) — [40] Stone AT, Knight MA, Nowack B. Speciation and
genotoxicity, biodistribution, and subchronic toxicity in chemical reactions of phosphonate chelating agents in
rats. Food Chem Toxicol 1988;26:601–10. aqueous media. In: Lipnick RL, Mason RP, Phillips ML,
[23] Francis MD, Centner RL. The development of dipho- Pittman CU, editors. Chemicals in the environment: fate,
sphonates as significant health care products. J Chem impacts and remediation, ACS Symposium Series No.
Educ 1978;55:760–6. 806. Washington, DC: American Chemical Society, 2001.
[24] Weiss J, H.agele G. Ion-chromatographic analysis of p. 59–94.
inorganic and organic complexing agents. Fresenius Z [41] Xyla AG, Mikroyannidis J, Koutsoukos PG. The
Anal Chem 1987;328:46–50. inhibition of calcium carbonate precipitation in aqueous
[25] Tsch.abunin G, Fischer P, Schwedt G. On the analysis of media by organophosphorous compounds. J Colloid
polymethylenephosphonic acids. I. A systematic survey of Interface Sci 1992;153:537–51.
the ion chromatography of organophosphonic acids. [42] Fischer K. Sorption of chelating agents (HEDP and
Fresenius Z Anal Chem 1989;333:111–6. NTA) onto mineral phases and sediments in aquatic
[26] Tsch.abunin G, Fischer P, Schwedt G. On the analysis of model systems, Part I: sorption onto clay minerals.
polymethylenephosphonic acids. II. A systematic survey Chemosphere 1991;22:15–27.
of post-column derivatization in ion chromatography. [43] Morillo E, Undabeytia T, Maqueda C. Adsorption of
Fresenius Z Anal Chem 1989;333:117–22. glyphosate on the clay mineral montmorillonite: effect of
[27] Vaeth E, Sladek P, Kenar K. Ion chromatography of Cu(II) in solution and adsorbed on the mineral. Environ
polyphosphates and phosphonates. Fresenius Z Anal Sci Technol 1997;31:3588–92.
Chem 1987;329:584–9. .
[44] Laiti E, Ohman .
L-O, Nordin J, Sjoberg S. Acid/base
[28] Tewari KMJ, van Stroe-Bieze SAM. Analysis of amine- properties and phenylphosphonic acid complexation at
containing phosphonates in detergent powders by anion- the aged d-Al2O3/water interface. J Colloid Interface Sci
exchange chromatography with pulsed amperometric 1995;175:230–8.
detection. J Chromatogr A 1997;771:155–61. .
[45] Laiti E, Ohmann L-O. Acid/ base properties and
[29] Thompson R, Grinberg N, Perpall H, Bicker G, Tway P. phenylphosphonic acid complexation at the boehmite/
Separation of organophosphonates by ion chromatogra- water interface. J Colloid Interface Sci 1996;183:
phy with indirect photometric detection. J Liquid 441–52.
Chromatogr 1994;17:2511–31. [46] Liu Y, Yu L, Guo J. Adsorption of PBTCA on alumina
[30] Shamsi SA, Danielson ND. Ribonucleotide electrolytes surfaces and its influence on the fractal characteristics of
for capillary electrophoresis of polyphosphates and sediments. J Colloid Interface Sci 2000;227:164–70.
polyphosphonates with indirect photometric detection. [47] Day GM, Hart BT, McKelvie ID, Beckett R. Influence of
Anal Chem 1995;67:1845–52. natural organic matter on the sorption of biocides
[31] Klinger J, Sacher F, Brauch H-J, Maier D. Determination onto goethite, II. Glyphosate. Environ Technol 1997;18:
of organic phosphonates in aqueous samples using liquid 781–94.
chromatography/ particle-beam mass spectrometry. Acta [48] Nowack B, Stone AT. Adsorption of phosphonates onto
Hydrochim Hydrobiol 1997;25:79–86. the goethite-water interface. J Colloid Interface Sci
[32] Nowack B. Determination of phosphonates in natural 1999;214:20–30.
waters by ion-pair high performance liquid chromato- [49] Nowack B, Stone AT. Influence of metals on the
graphy. J Chromatogr A 1997;773:139–46. adsorption of phosphonates onto goethite. Environ Sci
[33] Nowack B, Stone AT. Degradation of Nitrilotris(methy- Technol 1999;3:3627–33.
lenephosphonic acid) and related (amino)phosphonate [50] Jung A, Bisaz S, Fleisch H. The binding of pyropho-
chelating agents in the presence of manganese and sphate and two diphosphonates by hydroxyapatite
molecular oxygen. Environ Sci Technol 2000;34:4759–65. crystals. Calcif Tissue Res 1973;11:269–80.
[34] Nowack B. Determination of phosphonic acid breakdown [51] Chirby D, Franck S, Troutner DE. Adsorption of 153Sm-
products by high performance liquid chromatography EDTMP on calcium hydroxyapatite. Int J Radiat Appl
after derivatization. J Chromatogr A 2002;942:185–90. Instrum Part A 1988;39:495–9.
[35] Ammann AA. Determination of strong binding chelators [52] Black SN, Bromley LA, Davey RJ, Dobbs B, Rout JE.
and their metal complexes by anion-exchange chromato- Interactions at the organic/inorganic interface: binding
graphy and inductively coupled plasma mass spectro- motifs for phosphonates at the surface of barite crystals. J
metry. J Chromatogr A 2002;947:205–16. Chem Soc Faraday Trans 1991;87:3409–14.
[36] Ammann AA. Speciation of heavy metals in environ- [53] Horstmann B, Grohmann A. Investigations into the
mental water by ion chromatography coupled to ICP- biodegradability of phosphonates. Vom Wasser 1988;70:
MS. Anal Bioanal Chem 2002;372:448–52. 163–78.
 ARTICLE IN PRESS
B. Nowack / Water Research ] (]]]]) ]]]–]]] 13

[54] Fischer K. Sorption of chelating agents (HEDP and [70] Browning FH, Fogler HS. Effect of precipitating condi-
NTA) onto mineral phases and sediments in aquatic tions on the formation of calcium-HEDP precipitates.
model systems. Part II: Sorption onto sediments and Langmuir 1996;12:5231–8.
sewage sludges. Chemosphere 1992;24:51–62. [71] Friedfeld SJ, He S, Tomson MB. The temperature and
[55] Held S. Th environmental behavior of chelating agents on ionic strength dependence of the solubility product
phosphomic acid basis. Textilveredlung 1989;24:394–8. constant of ferrous phosphonate. Langmuir 1998;14:
.
[56] Nowack B, Lutzenkirchen J, Behra P, Sigg L. Modeling 3698–703.
the adsorption of metal-EDTA complexes onto oxides. [72] Zholnin AV, Zudov VG, Leitsin VA, Nosova RL,
Environ Sci Technol 1996;30:2397–405. Smirnov EN. Preparation of the iron complex of
[57] Stumm W. Reactivity at the mineral–water interface: nitrilotrimethylenephosphonic acid from zinc-production
dissolution and inhibition. Colloids Surf A 1997;120: wastes. J Appl Chem USSR 1990;63:751–4.
143–66. [73] Deluchat V, Serpaud B, Caullet C, Bollinger J-C.
[58] Davis JA, Kent DB, Rea BA, Maest AS, Garabedian SP. Protonation and complexation constants of 1-hydro-
Influence of redox environment and aqueous speciation xyethane-1,10 -diphosphonic acid (HEDP) with divalent
on metal transport in groundwater. In: Brown DS, editor. cations: a study of insoluble complexes of HEDP with
editor, Metals in groundwater. Boca Raton: Lewis Pb(II) and Cd(II). Phosphorous Sulfur Silicon 1995;
Publishers, 1993. p. 223–73. 104:81–92.
[59] Jardine PM, Jacobs GK, O’Dell JD. Unsaturated [74] Gratz AJ, Hillner PE. Poisoning of calcite growth viewed
transport processes in undisturbed heterogeneous porous in the atomic force microscope (AFM). J Cryst Growth
media: II. Co-contaminants. Soil Sci Soc Am J 1993; 1993;129:789–93.
57:954–62. [75] Gal J-Y, Bollinger JC, Tolosa H, Gache N. Calcium
.
[60] Muller G, Steber J, Waldhoff H. The effect of hydro- carbonate solubility: a reappraisal of scale formation and
xyethane diphosphonic acid on phosphate elimination inhibition. Talanta 1996;43:497–1509.
with FeCl3 and remobilization of heavy metals: results [76] Benton WJ, Collins IR, Grimsey IM, Parkinson GM,
from laboratory experiments and field trials. Vom Wasser Rodger SA. Nucleation, growth and inhibition of barium
1984;63:63–78. sulfate-controlled modification with organic and inor-
[61] Bordas F, Bourg ACM. Effect of complexing agents ganic additives. Faraday Discuss 1993;95:281–97.
(EDTA and ATMP) on the remobilization of heavy [77] Davis RV, Carter PW, Kamrath MA, Johnson DA, Reed
metals from a polluted river sediment. Aquat Geochem PE. The use of modern methods in the development of
1998;4:201–14. calcium carbonate inhibitors for cooling water systems.
[62] Lacour S, Deluchat V, Bollinger JC, Serpaud B. In: Amjad Z, editor. Mineral scale formation and
Complexation of trivalent cations (Al(III), Cr(III), inhibition. New York: Plenum Press, 1995. p. 33–46.
Fe(III)) with two phosphonic acids in the pH range of [78] Zieba A, Stehuraman G, Perez F, Nancollas GH,
fresh waters. Talanta 1998;46:999–1009. Cameron D. Influence of organic phosphonates on
.
[63] Muller .
G, Forstner U. Experimental mobilization of hydroxyapatite crystal growth kinetics. Langmuir 1996;
copper and zinc from aquatic sediments by some 12:2853–8.
polyphosphate substitutes in detergents. Z Wasser Ab- [79] Horstmann B, Grohmann A. The influence of phospho-
wasser Forsch 1976;9:150–2. nates on phosphate elimination. Part 1: 1-hydroxyethane-
[64] Browning FH, Fogler HS. Effect of synthesis parameters 1,1-diphosphonic acid (HEDP). Z Wasser Abwasser
on the properties of calcium phosphonate precipitates. Forsch 1984;17:177–81.
Langmuir 1995;11:4143–52. [80] Horstmann B, Grohmann A. The influence of phospho-
[65] Gerbino AJ.Quantifying the retention, release of poly- nates on phosphate elimination. Part 2: 2-phosphono-
phosphonates in oil and gas producing formations using butane-1,2,4-tricarbonic acid (PBTC), aminotri(methyle-
surface complexation and precipitation theory. Disserta- nephosphonic acid) (ATMP) and ethylenediamintetra(-
tion, Rice University, Texas, 1996. methylenephosphonic acid) (EDTMP). Z Wasser
[66] Samakaev RK, Dyatlova NM, Dytyuk LT. The solubility Abwasser Forsch 1986;19:236–40.
in water of the nitrilotrimethylenephosphonates of [81] Huang J, Chen R. An overview of recent advances on the
the group II elements. Russ J Inorg Chem 1984;29: synthesis and biological activity of a-aminophosphonic
1819–20. acid derivatives. Heteroatom Chem 2000;11:480–92.
[67] Oddo JE, Tomson MB. The solubility and stoichiometry [82] Horiguchi M, Kandatsu M. Isolation of 2-aminoethane
of calcium-diethylenetriaminepenta(methylene phospho- phosphonic acid from rumen protozoa. Nature
nate) at 70 C in brine solutions at 4.7 and 5.0 pH. Appl 1959;184:901–2.
Geochem 1990;5:527–32. [83] Wanner BL. Molecular genetics of carbon-phosphorous
[68] Kan AT, Oddo JE, Tomson MB. Formation of two bond cleavage in bacteria. Biodegradation 1994;5:175–84.
calcium diethylenetriaminepentakis(methylene phospho- [84] McMullan G, Quinn JP. The utilization of aminoalkyl
nic acid) precipitates and their physical chemical proper- phosphonic acids as sole nitrogen source by an environ-
ties. Langmuir 1994;10:1450–5. mental bacterial isolate. Lett Appl Microbiol
[69] Pairat R, Sumeath C, Browning FH, Fogler HS. 1993;17:135–8.
Precipitation and dissolution of calcium-ATMP precipi- [85] Schowanek D, Verstraete W. Phosphonate utilization by
tates for the inhibition of scale formation in porous bacterial cutures and enrichments from environmental
media. Langmuir 1997;13(1):791–1798. samples. Appl Environ Microbiol 1990;56:895–903.
 ARTICLE IN PRESS
14 B. Nowack / Water Research ] (]]]]) ]]]–]]]

[86] Raschke H, Rast H-G, Kleinstuck . R, Sicius H, Wischer [101] Klinger J, Sacher F, Brauch HJ, Maier D, Worch E.
D. Utilization of 2-phosphonobutane-1,2,3-tricarboxylic Behavior of phosphonic acids during drinking water
acid as source of phosphorous by environmental bacterial treatment. Vom Wasser 1998;91:15–27.
isolates. Chemosphere 1994;29:81–8. [102] Gilbert E, Hoffmann-Glewe S. Ozonation of ethylene-
[87] Schowanek D, Verstraete W. Phosphonate utilization by diaminetetraacetate (EDTA) in aqueous solution, influ-
bactaria in the presence of alternative phosphorous ence of pH value and metal ions. Water Res 1990;24:
sources. Biodegradation 1990;1:45–53. 39–44.
[88] Bolton H, Girvin DC. Effect of adsorption on the [103] Klinger J, Lang M, Sacher F, Brauch HJ, Maier D,
biodegradation of nitrilotriacetate by Chelatobacter Worch E. Formation of glyphosate and AMPA during
heintzii. Environ Sci Technol 1996;30:2057–65. ozonation of waters containing ethylenediaminetetra(-
[89] Zaranyika MF, Nyandoro MG. Degradation of glypho- methylenephosphonic acid). Ozone Sci Eng 1998;20:
sate in the aquatic environment: an enzymatic kinetic 99–110.
model that takes into account microbial degradation of [104] Deluchat V, Bollinger JC, Serpaud B, Caullet C. Divalent
both free and coloidal (or sediment) particle adsorbed cations speciation with three phosphonate ligands in the
glyphosate. J Agric Food Chem 1993;41:838–42. pH-range of natural waters. Talanta 1997;44:897–907.
.
[90] Nortemann B. Biodegradation of EDTA. Appl Microbiol [105] Lacour S, Deluchat V, Bollinger JC, Serpaud B. Influence
Biotechnol 1999;51:751–9. of carbonate and calcium ions on the phosphonate
[91] Kari FG, Giger W. Modeling the photochemical degra- complexation with Cu, Zn, Cd and Ni in fresh waters:
dation of EDTA in the River Glatt. Environ Sci Technol an evaluation of thermodynamic constants and a
1995;29:2814–27. chemical model. Environ Technol 1999;20:249–57.
[92] Fischer K. Distribution and elimination of HEDP in [106] Margerum DW. Exchange reactions of multidentate
aquatic test systems. Water Res 1993;27:85–493. ligand complexes. Rec Chem Prog 1963;24:237–51.
[93] Matthijs E, De Oude NT, Bolte M, Lemaire J. Photo- [107] Xue HB, Sigg L, Kari FG. Speciation of EDTA in
degradation of ferric ethylenediaminetetra(methylene- natural waters: exchange kinetics of FeEDTA in river
phosphonic acid) (EDTMP) in aqueous solution. Water water. Environ Sci Technol 1995;29:59–68.
Res 1989;23:845–51. [108] Deluchat-Antony V, Bollinger JC, Serpaud B, Caullet C.
[94] Lockhart HB, Blakeley RV. Aerobic photodegradation of Influence of some washing powder components on
X(N) chelates of ethylenedinitrilotetraacetate (EDTA): copper(II) and calcium(II) complexation with fulvic acids.
implications for natural waters. Environ Lett 1975;9: Int J Environ Anal Chem 1998;68:123–35.
19–31. [109] Sigg L, Xue HB. Metal speciation: concepts, analysis and
[95] Nowack B, Baumann U. Biodegradation of the photo- effects. In: Stumm W, editor. Chemistry of aquatic
lysis products of Fe(III)EDTA. Acta Hydrochim Hydro- systems: local and global perspectives. Brussels, Luxem-
biol 1998;26:104–8. bourg: ECSC, EEC, EAEC, 1994. p. 153–81.
[96] Martell AE, Motekaitis RJ, Fried AR, Wilson JS, [110] Nowack B, Xue HB, Sigg L. Influence of natural and
MacMillan DT. Thermal decomposition of EDTA, anthropogenic ligands on metal transport during infiltra-
NTA, and nitrilotrimethylenephosphonic acid in aqueous tion of river water to groundwater. Environ Sci Technol
solution. Can J Chem 1975;53:3471–6. 1997;31:866–72.
[97] Kaslina NA, Polyakova IA, Kessenikh AV, Zhadanov [111] Rizkalla EN. Metal chelates of phosphonate-containing
BV, Rudomino MV, Churilina NV, Kabachnik MI. ligands. Rev Inorg Chem 1983;5:223–304.
Thermal decomposition of nitrilotrimethylenephosphonic [112] Nowack B, Kari FG, Hilger SU, Sigg L. Determination
acid in aqueous solution. J Gen Chem USSR 1985; of adsorbed and dissolved EDTA-species in natural
55:472–5. waters. Anal Chem 1996;68:561–6.
[98] Tsch.abunin G, Fischer P, Schwedt G. On the analysis of [113] Nirel PM, Pardo PE, Landry JC, Revaclier R. Method
polymethylenephosphonic acids. III. Stability of ethylene- for EDTA speciation determination: application to
diaminetetramethylenephosphonic acod (EDTMP) in aqu- sewage treatment plant effluents. Water Res 1998;32:
eous solution. Fresenius Z Anal Chem 1989;333:123–8. 3615–20.
[99] Schowanek D, Verstraete W. Hydrolysis and free radical [114] Bedsworth WW, Sedlak DL. Determination of metal
mediated degradation of phosphonates. J Environ Qual complexes of ethylenediaminetetraacetate in the presence
1991;20:769–76. of organic matter by high-performance liquid chromato-
[100] Nowack B, Stone AT. Heterogeneous and homogeneous graphy. J Chromatogr A 2001;905:157–62.
oxidation of nitrilotrismethylenephoshonate (NTMP) in [115] Metzner G. Behavior of organic chelating agents on
the presence of oxygen and manganese (II, III). J Phys phosphonic acid basis in wastewater treatment plants.
Chem B 2002;106:6227–33. Beitr Abwasser Fisch Flussbiol 1990;44:323–36.