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 Commission Enterprise and Industry

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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 of surfactants; the biodegradation of main non-surfactant organic detergent ingredients.

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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)responsible 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 Dtergence et des Produits dEntretien),

CESIO (Comit Europen des Agents de Surface et de leurs Intermdiares Organiques)

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?uri=COM:2009:0230:FIN:en:PDF)
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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?SUBID=4) which concluded that:
the risk characterisation for LAS as expressed by the PEC/PNEC ratio was < 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/RiskAssessment.cfm?SUBID=34) 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 <1 (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 of surfactants;

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
Chemical ingredient Acids-Bases Bleaching agents, activators and stabilisers Builders, complexing agents and ion exchangers Corrosion inhibitors Dyes Dye transfer inhibitors Enzymes Fluorescent whitening agents Foam regulators Purpose To ensure optimal pH of wash water Enhanced cleaning performance Water-softening to maximise cleaning efficiency (i.e. removing dirt and keeping it in suspension) To prevent corrosion of washing machines To add colour to detergents To prevent loss of garment dyes Biological cleaning Optical brightening To limit foam generation (machine washing)

Formulation aids
Soil repellents/anti-redeposition agents Solvents
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To improve detergent performance

To prevent re-deposition of dirt during washing To keep ingredients in solution

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 was delivered in June 2006
(accessible at: http://ec.europa.eu/enterprise/chemicals/legislation/detergents/index_en.htm)

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 (I&I) 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(PVP): 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- difficult to conclude for enviromental risks (b) For PDMS: Few concerns over the risks associated with HMW-PDMS. 5. Anti-redeposition agents. Carboxymethyl-cellulose (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_scher/docs/scher_o_057.pdf)

SCHER concluded that the 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: (1) 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 I&I 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

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