David Berryman1, François Houde2

1 Ministère du Développement durable, de l’Environnement et des Parcs, Québec, QC, Canada. 2 Centre d’expertise en analyse environnementale du Québec, Québec, QC, Canada

0 20 km

Riv.Yamaska Sud-Est

Riv.

YamaskaNord

Saint-Victor

Plessisville

Cookshire

Acton Vale

GranbyFarnham

Cowansville

Lac

Saint-Pierre

Fleuve Saint-Laurent

Québec

Trois-Rivières

Sherbrooke

Riv

ière

Riv

ière

Rivière

Rivière

Rivière

Rivière

Rivière

Ric

helie

u

Yam

aska

Bécancour

Saint-

Saint-

L’Assomption

Chaudière

François

Maurice

Montréal

Riv.Yamaska Sud-Est

Riv.

YamaskaNord

Figure 5: Concentrations of nonylphenolic compounds in Eaton River downstream of Cookshire

Le Renne river (Acton Vale)

Eaton river (Cookshire)

Figure 2: Sampling water from a bridge.

A survey of nonylphenol ethoxylates in seven rivers of Quebec receiving treated textile effluents

Summary

A one-year (2002 - 2003) monthly survey in seven rivers of Quebec receiving treated textile effluents reveals occurrences of high concentrations of nonylphenol ethoxylates (NPEO) in these rivers. Chronic toxicity levels of Quebec’s water quality criteria for the protection of aquatic life were exceeded in 9 to 45 % of the samples, depending on sampling sites. Periods of very high concentrations (118 to 482 µg/l for NP1-17EO + NP1-2EC) have been detected in two rivers. These concentrations exceed the acute toxicity levels of Quebec’s water quality criteria for the protection of aquatic life for NPEO, as well as most data published in the scientific literature for these substances. High concentrations of NPEO occurred mostly in winter, as cold temperatures slows the biodegradation of these substances in wastewater treatment plants. This leads to incomplete degradation of NPEO and higher levels of degradation intermediates (NP1EO, NP2EO, NP1EC and NP2EC) reaching the end of the treatment chain and the receiving streams. Eight samples were filtrated and the liquid and solid phases analysed separately. The solid phase accounted for only 1 to 4 % of the total NPEO in the samples. Provincial and federal governments have taken measures to curtail the use of NPEO in Canadian industries. This should lead to decreases in levels of these substances in Quebec’s rivers by the end of 2009.

Results

• Downstream of the towns, concentrations for the sum of the 19 substances (NP1-17EO + NP1-2EC) range from 0,04 to 482 µg/1. Site medians range from 1,19 to 20,8 µg/l (table 2 and figure 3).

• Concentrations upstream of the towns are low : < DL to 0,7 µg/l (table 2).

• High concentrations occur mostly in winter (e.g.: figures 4 and 5) as biodegradation of NPEOs in WWTP is slowed down in cold water.

• During winter, at most sites (Cookshire, Granby, Acton Vale and Plessisville), concentrations exceed the chronic level of water quality criteria for aquatic life in 2 to 4 consecutive monthly samples. This strongly suggests that winter highs are maintained for periods that are long enough to have negative effects on aquatic life.

• At two sites (Cookshire and Acton Vale) February and March concentrations are in the 100 - 500 µg/l range (figures 4 and 5), exceeding the acute level of water quality criteria for the protection of aquatic life as well as most data published in the scientific literature according to reviews by Ying et al., 2002 and Kneeper et al., 2003.

• In summer samples, carboxylates (NP1-2EC) account for 65 % of the total (NP1-17EO + NP1-2EC), while in winter, they account for 19 %. This means that NPEO surveys that do not include carboxylates may be missing a significant part of the nonylphenolic compounds.

• Quality assurance included five blanks, six duplicates and eight samples that were filtrated (0,7 µm) and the solid and liquid phases analysed separately. Nonylphenolic compounds in the solid phase accounted for less that 4 % of the total. Thus, it is not worth doubling the analysis budget of the survey with separate analysis. Four of the five blanks had results < DL for all NPEOs and NPECs, while the other one had only traces of four compounds summing up to 0,14 µg/l. This proves that procedural contamination was minimal. Duplicates were two successive samples taken from the same water body. In four cases, differences between the two duplicates were < 1 µg/l for the sum of the 19 substances. Differences in the two other pairs were more important (12,4 vs. 15,4 and 17,3 vs. 22,3 µg/l), but remain acceptable considering the fact that they include short term variations in the concentrations of NPEOs in the water body.

References

Berryman D., F. Houde, C. DeBlois, M. O’Shea, 2004. Nonylphenolic coumpounds in drinking and surface waters downstream of treated textile and pulp and paper effluents: a survey and preliminary assessment of their potential effects on public health and aquatic life. Chemosphere 56 (2004) 247-255.Birch, R.R., 1991. Prediction of the fate of detergent chemicals during sewage treatment. J. Chemical Technol. Biotech. 50, 411-422.CCME, 2001. Canadian Water Quality Guidelines for the Protection of Aquatic Life: Nonylphenol and it’s Ethoxylates. In: Canadian environmental quality guidelines, 1999, Canadian Council of Ministers of the Environment, Winnipeg, Canada.Environment Canada and Health Canada, 2001. Nonylphenol and its Ethoxylates. Priority Substances List Assessment Report. Report no EN 40-215-/57E, 98 p.Houde, F., DeBlois, C., Berryman, D. 2002. Liquid chromatography-tandem mass spectrometry determination of alkylphenol polyethoxylates and alkylphenol carboxylic acids in surface water. J. Chromato. A 961 (2), 245-256.Kneeper, T.P., Petrovic, M., de Voogt, P., 2003. Occurrence of surfactants in surface waters and freshwater sediments − 1. Alkylphenol ethoxylates and their derivative products. In : Kneeper, T.P., Barceló, D., de Voogt, P. (Eds.) Analysis and fate of surfactants in the aquatic environment (Wilson and Wilson’s comprehensive analytical chemistry; vol. 40). Elesvier, Amsterdam, The Netherlands, pp. 675-693.Mann, A.H., Reid, V.W., 1971. Biodegradation of synthetic detergents. Evaluation by community trials. Part 2: alcohol and alkylphenol ethoxylates. J. of American Oil Chemistry. 17, 650-654.Manzano, M.M., Perales, J.A., Sales, D., Quiroga, J.M., 1999. The effect of temperature on the biodegradation of a nonylphenol polyethoxylate in river water. Wat. Res. J. 33 (11), 2593-2600.Stiff, M.J., Rootham, R.C, Culley, G.E., 1973. The effects of temperature on the removal on non-ionic surfactants during small-scale activated-sludge sewage treatment – I. Comparison of alcohol ethoxylates with a branched-chain alkyl phenol ethoxylate. Wat. Res. J. 7, 1003-1010.Ying, G., Williams, B., Kookana, R., 2002. Environmental fate of alkylphenols and alkylphenol ethoxylates − a review. Environmental International, 28, 215-226.

Introduction and objective

A previous survey of NPEOS at eleven drinking water treatment plants in Quebec (Berryman et al., 2004) confirmed results of other studies showing that drinking water is not a significant route of human exposure to these substances. Food and personal care products account for exposures that are orders of magnitude higher (Environment Canada and Health Canada, 2001). However, in this first survey, results in raw (untreated) water sometimes exceeded water quality criteria for the protection of aquatic life. Since drinking water intakes are usually located in river reaches that are minimally exposed to pollution, it was hypothesised that concentrations of NPEOs could much higher in streams directly exposed to the major sources of these substances. In Quebec, textile plants are known to be important users of NPEOs. Thus, the objective of the second survey was to measure the concentrations of NPEOs in streams receiving treated textile effluents and to evaluate the associated potential impact on aquatic life.

Methods

• Water samples taken monthly (July 2002- June 2003) at seven sites downstream of towns with textile plants (figure 1). Samples taken twice upstream of the towns. Effluents of the textile plants are treated by the municipal waste water treatment plants (WWTP). • Most sampling carried out from bridges (figure 2) located 50 to 3 000 m from the WWTP effluent.• Sample analysis by liquid chromatography - tandem mass spectrometry (LCMSMS), leading to individual results for 17 NPEO (NP1EO to NP17EO) and 2 NPEC (NP1EC and NP2EC) (Houde et al, 2002). • Data for the 17 NPEO summed up and compared to the Quebec’s water quality criterion for the protection of aquatic life of 12 µg/l (chronic) and 280 µg/l (acute) for NPEOs.• Data for the 17 NPEOs and 2 NPECs transformed into nonylphenol (NP) equivalents (table 1) and compared to the Quebec’s water quality criterion for the protection of aquatic life of 6 µg/l (chronic) and 29 µg/l (acute) for NP.

• Downstream of towns with textile plants, river concentrations of nonylphenolic compounds are often too high during winter months. Chronic levels of NPEO water quality guidelines for the protection of aquatic life are often exceeded and even the acute toxicity levels are sometimes exceeded. This is explained by the slower degradation of NPEOs in cold water, which leads to larger quantities of degradation intermediates reaching the end of the WWTP treatment chain and being discharged into the receiving water bodies.

• The above conclusion must not be extrapolated to all towns with textile plants. Many plants do not use NPEOs and many have dry processes.

• Measures have been taken by the provincial and federal governments to reduce the use of NPEOs. Namely, the federal government requires that by the end of 2009, all industrial users of NPEO must have reduced their use of these substances by 97 % from the quantity they used in 1998. This survey should be repeated in 2010 to verify if NPEO levels in rivers have been taken down to safer levels.

• Surveys of NPEOs should include carboxylated forms (NPECs), which can account for a large part of the nonylphenolic compounds found in rivers. In rivers with normal levels of suspended matter, NPEOs in the solid phase account for only a small part (< 4 %) of the total. Thus, in such conditions, it is not worth filtrating the samples and doubling the analysis costs with separate analysis of the solid and liquid phases.

0

100

200

300

400

500

600

Jul Sept Oct Nov Dec Jan Feb Mar Apr May Jun

Con

cent

ratio

n(µ

g/l)

NP1-17EO + NP1-2EC

0

20

40

60

80

100

120

140

160NP1-17EO + NP1-2EC

Jul Sept Oct Nov Dec Jan Feb Mar Apr May Jun

Con

cent

ratio

n(µ

g/l)

Table 2: Concentrations (µg/l) of nonylphenolic compounds (NP1-17EO + NP1-2EC) at the 14 sampling sites.

Conclusions

Saint-Victor0

20

40

60

80

100

120

140

160

CookshireCowansville

FarnhamGranby

Acton ValePlessisville

max 447

Maximum

75e centile

Median

25e centile

Minimum

Con

cent

ratio

n(µ

g/l)

Figure 4: Concentrations of nonylphenolic compounds in Le Renne River downstream of Acton Vale

Figure 3: Total concentrations of nonylphenols compounds (NP1-17EO+NP1-2EC) at the 7 downstream sites

Figure 1: Sampling sites

EquivalencyFactor

1

0,5

0,005

0,005

0,005

NP2EC

Compound

NP

NPnEO (1

≤

n

≤

8)

NPnEO (n > 8)

NP1EC

Table 1: Toxic equivalency factors for NP, NPEOs and NPECs (source : CCME, 2001)

Full report: www.mddep.gouv.qc.ca/eco_aqua/nonylphenol/nonyl-textile.htmdavid.berryman@mddep.gouv.qc.ca