Prsentation PowerPoint

1
Anaerobic biodegradation of surfactants and
non-surfactant organic ingredients
in detergents (Commission reports under the
Detergents Regulation (EC) No 648/2004)
TAIEX Workshop on the Implementation of EU
Detergents Regulation Bucharest, 21 - 22
September 2009
European CommissionEnterprise and Industry
2
COM reports under Article 16(2) of (EC) No
648/2004
Article 16(2) of Regulation (EC) No 648/2004 on
detergents lays down that By 8 April 2009,
the Commission shall carry out a review of the
application of this Regulation, paying
particular regard to the biodegradability of
surfactants, and shall evaluate, submit a report
on, and, where justified, present legislative
proposals relating to
? anaerobic biodegradation ? the biodegradation
of main non-surfactant organic detergent
ingredients.
1 OJ L104, 8.4.2004, p. 1
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Consultation with stakeholders on the COM reports
?The various COM studies on both anaerobic
biodegradation and non surfactant organic
ingredients were performed by external
contractors. The final studies were evaluated
by the Commissions Scientific Committee on
Health and Environmental Risks (SCHER), the
scientific opinions of which served as the
basis of the COM reports.
? The findings of both COM studies and SCHER
opinions were discussed at several
meetings (2006-2008) of the COM Detergents
Working Group (MS representatives)responsi
ble for implementation of Detergents Regulation.
? The Detergents meetings were attended also by
Representatives of related industry
associations such as AISE (Association de la
Savonnerie, de la Détergence et des Produits
dEntretien), CESIO (Comité Européen des
Agents de Surface et de leurs Intermédiares
Organiques) ERASM (European Risk Assessment
and Management) etc. The positions and
submitted material by IND, MS and any other
interested parties were carefully considered
and were reflected in the COM reports
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COM (2009)230 report on Anaerobic biodegradation

• ? Detergents Regulation sets ultimate aerobic
  biodegradability as the main criterion for use of
  surfactants in detergents.
• ? Anaerobic biodegradation of surfactants in
  sludge and sediment produces CH4 (in contrast to
  the CO2 produced under aerobic conditions found
  in waste and surface water).

The COM report on anaerobic biodegradation of
detergent surfactants focus on linear
alkylbenzene sulphonate (LAS) which is a
widely-used, poorly biodegradable surfactant
under anaerobic conditions. A review of
anaerobic testing methodology is also given.
COM (2009)230 report available at
http//eur-lex.europa.eu/LexUriServ/LexUriServ.do
?uriCOM20090230FINenPDF)
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Background studies on Anaerobic biodegradation
The Fraunhofer report (2003) assessed the
environmental impact in the EU resulting
from the incomplete biodegradation of detergent
surfactants under anaerobic conditions.
(http//ec.europa.eu/enterprise/sectors/chemicals/
documents/competitiveness/anaerobic_en.htm The
Fraunhofer study mainly concluded that
? The surfactants must be ultimately and readily
biodegradable under aerobic conditions in
order to prevent adverse environmental impacts.
? The poor biodegradability of some surfactants
(e.g. LAS) under anaerobic conditions may
sometimes result in a significant surfactant
content in sewage sludge, especially after
treatment in waste water treatment plants (WWTP)
employing an anaerobic sludge stabilisation
process.
? With regard to sediments, no accumulation of
aerobically ready biodegradable surfactants
has been observed, (such as of LAS over a period
of decades. Aerobic (rather than anaerobic)
biodegradation plays the main role in
elimination of organic compounds.
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2005 SCHER opinion on Anaerobic biodegradation
?The Fraunhofer study was evaluated by SCHER that
published an opinion in November 2005
(http//ec.europa.eu/health/ph_risk/committees/04_
scher/docs/scher_o_021.pdf)
? SCHER agreed with the main Fraunhofer
conclusion that The requirement for ready and
ultimate biodegradability of surfactants under
anaerobic conditions is not by itself regarded as
an effective measure for environmental
protection.
? However, SCHER expressed concerns about (a)
a potential for risk from LAS in sludge in
certain applications of worst case
environmental conditions (PEC/PNEC values
slightly above 1) (b) the relatively high
measured levels (0.5-1 g/kg) of other surfactants
in sewage sludge,including some
anaerobically biodegradable, such as
alcohol ethoxylates (AE) and alkyl phenol
ethoxylates (APE). (c) the fact that a single
test is not sufficient to evaluate anaerobic
biodegradability. A combination of several
tests is more appropriate.
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Latest scientific evidence on Anaerobic
biodegradation
?In reaction to the concerns expressed in the
2005 SCHER opinion, European Surfactant Industry
(CESIO) funded additional soil toxicity studies,
the results of which were published on an
updated 2007 HERA report on LAS
(http//www.heraproject.com/RiskAssessment.cfm?SU
BID4) which concluded that
the risk characterisation for LAS as expressed
by the PEC/PNEC ratio was lt 1 for all
environmental compartments, considering the
recently reported PNEC values (35
mg/kg versus 4.6 mg/kg in previous assessments)
so that lower PEC/PNEC ratios would indicate
no adverse environmental risks
? Concerning AE, a HERA report was produced in
May 2007 (http//www.heraproject.com/RiskAssessmen
t.cfm?SUBID34) according to which AE usage
in laundry cleaners and household cleaning
products is not a cause for concern for the
environment (in particular surface water,
sediment, sewage treatment facilities, and soil).
? In parallel, additional scientific findings on
LAS and anaerobic biodegradation were
published by several researchers such as Temnik
and. Klapwijk (2004, Krogh et al., (2007),
Jensen et al., (2007) Schowanek (2007), and Berna
(2007).
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2008 SCHER opinion on anaerobic biodegradation
In March 2008, the Commission (DG Enterprise
Industry) requested SCHER (1) to assess recent
HERA reports on LAS and AE and comment on their
conclusions concerning the environmental risks
(2) in the light of all available scientific
evidence, to reconfirm the key statements of
2005 SCHER opinion on anaerobic biodegradation of
surfactants/environmental protection (3) to
review the issue of anaerobic test methodology
for surfactants.
In November 2008, SCHER published its opinion
concerning anaerobic degradation of surfactants
(available at http//ec.europa.eu/health/ph_risk
/committees/04_scher/docs/scher_o_109.pdf)
(I) SCHER evaluation of HERA report on
alcohol-ethoxylates (AEs) ? The SCHER
considered the exposure assessment as generally
acceptable. ? The PEC/PNEC-ratios for AE are
sufficiently lower lt1 (surface water 0.041,
sediment 0.316, sewage treatment plant 0.007
and soil 0.103). ? Any remaining uncertainties
(e.g no consideration on AE-homologues) do not
invalidate the main HERA conclusion for no
environmental risks.
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(II) 2008 SCHER evaluation of HERA report on
LAS

• ? Overall, SCHER agreed with the proposed PNEC
  values for aquatic organisms and sediments.
• ? However, SCHER considered that a proper
  evaluation of the relevance of LAS
• effects on microbial activity is essential
  for a proper PNEC soil derivation. Unless
  additional justification can be provided, it is
  suggested to maintain the previous PNECsoil of
  4.6 mg/kg (and not the PNEC value of 35 mg/kg,
  recently proposed by HERA ).
• ? Recent environmental data seem to show a
  potential for degradation of LAS under anaerobic
  conditions in the environment.

Furthermore, due to lack of new evidence, SCHER
did not change the conclusion of its 2005
opinion that Poor biodegradability under
anaerobic conditions is not expected to produce
substantial modifications in the risk for
freshwater ecosystems as the surfactant removal
in the WWTP seems to be determined by its aerobic
biodegradability
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(III) 2008 SCHER opinion on Anaerobic testing
methodology

• ? The SCHER reviewed the existing screening and
  simulation test methods to determine ultimate
  anaerobic biodegradability of organic substances.
  (screening test OECD 311 simulation tests-TG
  307,308 ).
• ? Overall, SCHER believes that the existing
  OECD methods for anaerobic biodegradation
  together provide an appropriate methodology for
  the assessment of the anaerobic biodegradability
  of organic compounds.
• ? However, due to stringent (methanogenic)
  conditions used in the laboratory tests,
  inhibitory effects cannot be excluded therefore
  that a poor result may not be a final proof of
  anaerobic recalcitrance.

• ? In February 2009, CESIO (ERASM) informed of
  their initiative to
• undertake further research in order
• - to develop an improved method for measuring the
  anaerobic biodegradability
• under sludge digester condition, and
• to evaluate the LAS degradation in sediments and
  review any scientific
• evidence in order to precisely estimate the PEC
  value for LAS.

?The COM (2009)230 report notes that Once
sufficient, published evidence (e.g in a HERA
report or in literature) will be available,
an updated SCHER opinion would be requested in
the future.
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Conclusions of COM report on Anaerobic
biodegradation
?The lack of anaerobic degradation of
surfactants in various anaerobic compartments
does not seem to be correlated with any apparent
environmental risk. It can therefore be
concluded that anaerobic biodegradability should
not be used as an additional pass/fail
criterion for environmental acceptability of
surfactants such as LAS which are readily
biodegradable under aerobic conditions.
? The remaining concerns focus on the possible
environmental toxicity of surfactants, rather
than on their biodegradability (e.g calculations
for new PNECsoil for LAS) At present, there is
no evidence to justify legislative measures at EU
level, such as regulatory limit values for LAS
or other surfactants in sludge. However, once
further, sufficient, published evidence (e.g a
HERA report or in literature) will be
available, an updated SCHER opinion would be
requested in the future.
? The information requirements of the REACH
registration dossiers will ensure that
comprehensive data on the health and
environmental effects of detergents surfactants
will be submitted by industry to the European
Chemical Agency by December 2010. The REACH
registration information should be sufficient to
decide whether restrictions on certain
surfactants in detergents are needed on
environmental grounds, others than already
imposed by (EC) 648/2004.
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COM reports under Article 16(2) of (EC) No
648/2004
Article 16(2) of Regulation (EC) No 648/2004 on
detergents lays down that By 8 April 2009,
the Commission shall carry out a review of the
application of this Regulation, paying
particular regard to the biodegradability of
surfactants, and shall evaluate, submit a report
on, and, where justified, present legislative
proposals relating to ? anaerobic
biodegradation
1 OJ L104, 8.4.2004, p. 1
? the biodegradation of main non-surfactant
organic detergent ingredients.
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COM (2009)208 - Non-surfactant organic detergent
ingredients
This report presents the results of the
Commission's review on the biodegradation of the
main non-surfactant organic detergent ingredients
Table 1 Non-surfactant Detergent Ingredients

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RPA study (2006) - Non-surfactant organic
detergent ingredients
? Risk Policy Analysts Ltd (RPA) was contracted
by the Commission in order to fill the
data gaps concerning properties and environmental
impacts for the main non-surfactant organic
detergent ingredients. The final RPA report
(accessible at http//ec.europa.eu/enterprise/che
micals/legislation/detergents/index_en.htm)
was delivered in June 2006, and served as the
basis for the COM review.
? The RPA study examined the properties of about
50 representative detergent ingredients
? The substances which are readily biodegradable
with no other properties of potential
concern (such as high aquatic toxicity) were not
analysed further ? The substances (or groups)
retained for further analysis were those that are
not readily biodegradable (or they have
properties of potential concern). ? The
screening exercise of RPA resulted in a list of
specific substances and substance groups
of potential concern being selected for further
analysis, based on scientific evidence from
the various risk assessments.
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RPA study (2006) - detergent ingredients of
potential concern
1. Builders, Complexing Agents and Ion Exchangers
Phosphonates Slowly degradable.They may present
a environmental risk due to potential aquatic
chronic toxicity of HEDP (1- hydroxy ethane
diphosphonic acid) and its salts to Daphnia.
Polycarboxylates Not readily biodegradable. As
there are no available monitoring data,
concentrations in sludge-treated soils may be
significant.
EDTA and its salts EDTA and its salts may be
of concern to the environment with regard to
their use in industrial and institutional (II)
cleaning - but not for household detergents
where their use is limited.
Nitrilotriacetic acid (NTA) NTA is readily
biodegradable using a range of standard tests
although, in some cases, the formation of
metal-NTA complexes may slow the rate of
degradation.
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RPA study (2006) - detergent ingredients of
potential concern
2. Dye transfer inhibitors. Polyvinylpyrrolidone(P
VP) Further data would be desirable to
demonstrate that PVP presents no significant
environmental risks.
3. Fluorescent whitening agent. FWA-5 On basis
of its PNEC value, FWA-5 is unlikely to present
significant environmental risks. However, there
remains the possibility that the degradation
products are of potential concern.
4. Foam regulators. (a) For n-paraffins
available data on aquatic toxicity and
bioaccumulation highly uncertain-which difficult
to conclude for envir risks (b) For PDMS Few
concerns over the risks associated with HMW-PDMS.
5. Anti-redeposition agents. Carboxymethyl-cellulo
se (CMC) Further data on its environmental
levels would be needed to exclude potential
risks.
6. Solvents. 1-decanol and triethanolamine
Further data are required to reach a firm
conclusion on whether triethanolamine is likely
to be of concern.
Overall, RPA analysis concluded that even
persistent ingredients may not pose risks for the
environment (i.e. the PEC/PNEC ratio is less than
one) due to environmental degradation and/or low
environmental toxicity.
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2007 SCHER opinion on the RPA study
? In December 2006, the Commission requested
SCHER to assess the overall scientific quality
of the RPA report, and comment whether the RPA
conclusions are valid and in agreement with
existing literature. In June 2007, after
considering all the available evidence SCHER
published an opinion (available at
http//ec.europa.eu/health/ph_risk/committees/04_s
cher/docs/scher_o_057.pdf)
? SCHER concluded that overall quality of the RPA
study was good and agreed that this constitutes a
reliable factual basis concerning non-surfactant
organic ingredients in detergent formulations.
Concerning the biodegradation properties and
environmental risks of the most important
builders

• EDTA and salts SCHER confirmed that there is
  no risk from the use of EDTA in household
  detergents, whilst for some other applications
  (industrial detergents, paper mills, circuit
  board producers etc) a more precise exposure
  assessment is needed to exclude potential risks.

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2007 SCHER opinion on the RPA study
(2) Nitrilotriacetic Acid (NTA and salts) SCHER
concluded that there are no environmental risks
for all production and use patterns. Although
there is an evidence of carcinogenicity in rats
and mice, no such human data is available.
(3) Phosphonates SCHER concluded that a
potential risk for phosphonates used in
zeolite-based (phosphate-free) compact powers
has been identified for the aquatic and
terrestrial (agricultural soil) compartments.
SCHER underlined that the persistence of
phosphonates and the inconsistencies regarding
its bioaccumulation potential recommend a further
assessment of long-term and secondary poisoning.
(4) Polycarboxylates SCHER concluded that a
potential risk may exist due to polycarboxylates
used in zeolite-based detergent formulations for
aquatic organisms as the validity of data for
chronic NOEC could not be confirmed, while
uncertainties also exist for terrestrial
organisms as there is no enough information for
estimating a PNEC.
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Further investigation on polycarboxylates
? According to AISE, an increased consumption of
polycarboxylates (PCXs) in the EU (to 80.000 in
2007 from 50 000 t/y in 2004) is linked to the
increasing move towards the use of
phosphate-free laundry detergents and the
associated product re-formulation.
? New scientific information on PCxs (including
its homo- copolymers P(AA-MA) of acrylic-maleic
acid) became available towards end of 2007 in
the form of a targeted HERA report (not
considered by 2007 SCHER opinion), concluding
that the use of PCxs in detergents does not
pose environmental risks(excepting P-AA/MA in
soil-local)
? In November 2008, SCHER adopted a new opinion
indicating that the changes in the PNECaquatic
proposed by HERA for P-AA/MA have consequences
for the outcome of the risk assessment. However,
SCHER could not provide a final answer on the
potential environmental risk due to the lack of
information on the reliability of fish chronic
studies and on soil microbial functions,
essential for the RA of the PCXs.
? Based on new data from BASF Company
demonstrating that for P-AA/MA the PEC/PNEC for
all environmental compartments is below 1, and
that there is no risk from P-AA/MA for
terrestrial organisms, an updated 2009 HERA
report was produced and resubmitted to SCHER in
April 2009. SCHER is in the process of finalising
an updated scientific opinion on PCXs, though it
seems that some of their concerns for the
environmental fate of these compounds are
maintained.
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Conclusions of COM report on organic detergent
ingredients
? Although no significant risks to the
environment have been identified for any of the
non-surfactant organic detergent ingredients,
uncertainties due to insufficient data, remain
concerning the environmental fate of (a)
polycarboxylates and phosphonates, (b) EDTA and
its salts (mainly in II detergents),
triethanolamine, FWA-5 and paraffins.
? The REACH registration information should be
sufficient to decide whether restrictions on the
above-mentioned detergent organic ingredients are
needed on environmental grounds at EU level, and
if so, these could be imposed under the REACH
restriction procedures.
? For polycarboxylates, a revision is ongoing
(based on updated SCHER opinion and identified
needs for further investigation that IND may
undertake ). In addition, EDTA as a priority
substance in Annex III of Directive 2008/105
would be further evaluated within WFD framework
by 2011.

• Consequently, the review of the Commission did
  not conclude a need for proposing further
  legislation at this point concerning
  non-surfactant organic ingredients in detergents.

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Anaerobic biodegradation of surfactants and
non-surfactant organic ingredients
in detergents (Commission reports under the
Detergents Regulation (EC) No 648/2004)
TAIEX Workshop on the Implementation of EU
Detergents Regulation Bucharest, 21 - 22
September 2009
European CommissionEnterprise and Industry