Characterization of Ecotoxicological Effects of Green Liquor Dregs

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Characterization of ecotoxicological effects of green liquor dregs from the pulp and paper industry Beatriz Bandarra, Luciano Gomes, Joana Luísa Pereira, Fernando J. M. Gonçalves, Rui C. Martins, and Margarida J Quina ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/acssuschemeng.9b02636 • Publication Date (Web): 29 Jul 2019 Downloaded from pubs.acs.org on August 1, 2019

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ACS Sustainable Chemistry & Engineering

Characterization of ecotoxicological effects of green liquor dregs from the pulp and paper industry Beatriz S. Bandarra1, Luciano A. Gomes1,2, Joana L. Pereira3, Fernando J.M. Gonçalves3, Rui C. Martins1, Margarida J. Quina1,* 1CIEPQPF,

Chemical Process Engineering and Forest Products Research Centre. Department of Chemical Engineering, University of Coimbra, Rua Sílvio Lima, Pólo II, 3030-790 Coimbra, Portugal; 2IFB - Federal Institute of Education, Science and Technology of Brasília - IFB, Campus Ceilândia, Brasília Federal District, QNN 26 Área Especial - Ceilândia, Brasília - DF, 72220-260, Brazil; 3CESAM, Department of Biology, University of Aveiro, Campus Universitário de Santiago 3810-193 Aveiro, Portugal; *Corresponding author: [email protected]

Abstract Green liquor dregs (GLD) are a major waste of the pulp and paper industry, and its correct classification is important to find alternatives to landfill disposal. In the European Union, the methodology to determine the hazard property HP 14 (“ecotoxic”) is under discussion. Although biological tests are likely more representative of wastes environmental behavior, there are still no official guidelines on procedures, and ecotoxicity classification relies on the chemical composition. This work aimed to evaluate the ecotoxicity of GLD to determine HP 14. The assessment comprised a chemical analysis (using ClassifyMyWasteTM software) and a battery of biotests targeting aquatic ecosystems (Lepidium sativum, Aliivibrio fischeri, Raphidocelis subcapitata, Lemna minor and Daphnia magna). The chemical analysis denoted GLD as of “Possible Hazard” while the battery of biotests showed high ecotoxic effects for 3 out of 5 organisms, the most sensitive being Lepidium sativum, Lemna minor and Daphnia magna. The pH correction of tested eluates to neutral values did not modulate the noticed effects. Globally, the results suggest that GLD should be classified as ecotoxic. Though, the European waste legislation should provide guidelines to apply the end-of-waste criteria and avoid landfilling even for materials like GLD. Keywords: ecotoxicological effect; green liquor dregs; HP 14; aquatic organisms; chemical classification.

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Introduction Pulp and paper industry is an important economic sector in several countries and in Portugal as well. This industry uses wood as the main raw material and several chemicals for separating the cellulose fibers. Due to economic and environmental reasons, the Kraft pulp mills include specific circuits for chemicals recovery, namely the causticizing process for reacting sodium carbonate and regenerating sodium hydroxide.1 Despite all efforts for closing the process loops, the pulp and paper industry originates about 11 Mt of wastes per year in Europe, which accounts for about 11% of the total paper production.2 As a result, this industry is one of the major producers of solid and semi-solid wastes,1 namely green liquor dregs (GLD).2,3 GLD results from the causticizing process (known as the chemical recovery cycle) and corresponds to the non-soluble compounds from the clarification of the green liquor.1 This inorganic material is mostly composed of small grey particles4 containing sulfides, sodium hydroxide, sodium carbonate, calcium carbonate, unburned carbon and traces of heavy metals.5 The amount and chemical composition of GLD depend on the raw materials, the process technology, operating conditions and the properties of the pulp to be obtained.2 It presents high natural pH, in the range of 10-13,5-7 high buffering capacity (or acid neutralization capacity) and reduced hydraulic conductivity.8,9 Nowadays, GLD is mostly landfilled after dewatering and drying.2,10 However, its management has become an economic and environmental concern11 since landfill space has been reduced and associated costs increased.1 Indeed, although the use of GLD is still limited,12 potential applications have been studied in order to reduce disposal needs.4 Potential applications of GLD include the neutralization of acidic soils,1, 13 the neutralization of acidic wastewater,4 the control of the acid mine drainage,10 covering material,14 cement production,15 and the production of eco-friendly geopolymer mortars.16 Anyway, some restrictions are applied to its utilization due to the classification as waste instead of secondary raw material. Still, the Waste Framework Directive (Directive 2008/98/EC of the European Parliament and of the Council) lists the criteria for the end-of-waste status (Article 6), i.e., the criteria for a waste to cease to be a waste and becoming a by-product on the terms of the Article 5. For this to happen, the use of the material cannot cause negative effects on the environment or human health. Thus, it is important to characterize and classify wastes to avoid disposal in landfills following a circular economy paradigm. According to the European List of Waste (LoW), GLD is a non-hazardous waste with the code 03 03 02. Moreover, the Confederation of European Paper Industry (CEPI) considers that wastes produced by the pulp and paper industry are non-hazardous and can be disposed of 2 ACS Paragon Plus Environment

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safely.17 However, most of the aquatic life has a pH tolerance within the range of 6.5-9 on a long-term basis.18 Thus, and regardless of the official classification, the high basic nature of GLD was hypothesized to be potentially harmful to these ecosystems, primarily motivating the present study. In the European Union (EU), the potential environmental effects of wastes are evaluated according to the hazard property HP 14 (“ecotoxic”). Directive 2008/98/EC defines HP 14 as “waste which presents or may present immediate or delayed risks for one or more sectors of the environment”. The Commission Regulation (EU) No 1357/2014 (replacing Annex III to Directive 2008/98/EC) classifies a waste as hazardous if exhibits at least one of the 15 hazard properties covered by this regulatory document. The definition of a methodology to assess HP 14 has been a challenge in the framework of EU waste legislation. Although the EU waste legislation was revised in 2014 to promote a harmonized classification of wastes based on the chemicals legislation (with respect to classification, labelling and packaging – CLP; Regulation (EC) No 1272/2008),19 only in 2017 the Council Regulation (EU) 2017/997 amended Annex III to Directive 2008/98/EC regarding HP 14. Hereupon, recommendations were given on how to align the evaluation of HP 14 with CLP, presenting the calculation formulas and the limit values that should be used to estimate ecotoxicity based on wastes chemical composition. On the other hand, there are no official recommendations at the EU level on how to carry out biological tests to assess rather than solely predict HP 14 (Commission notice 2018/C 124/01), despite the results of these tests should predominate over the results of methods based on chemical composition (Commission Decision 2014/955/EU, amending Decision 2000/532/EC on the list of waste). Therefore, it is reasonable to understand that GLD classification as a nonhazardous waste derives only from the prediction based on chemical properties rather than integrates results yield by actual testing with model organisms. Still, some batteries of biotests have been proposed in the literature complying with HP14 assessment.20,

21, 22, 23, 24

Moreover, criteria to classify wastes regarding HP 14, integrating

biotest results, have been discussed. 23, 25, 26, 27, 28, 29 Experimental tests using organisms account for the effects of all substances burdening the waste (often tested after extraction with water), the potential interactions (e.g., synergistic and antagonistic) but only in the fraction of the waste which is bioavailable.30 On the contrary, the regulatory approach based on chemical composition only accounts for the total element concentration and does not consider the interactions between components. Moreover, it is important to note that wastes are frequently a complex and variable mixture and their full composition is often unknown,30 whereas CLP concerns to pure chemicals and mixtures of pure chemicals.19 For this reason, the worst-case 3 ACS Paragon Plus Environment


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scenario is frequently considered in the chemical approach to assess HP 14. This scenario considers that the elements present in the waste correspond to the chemical species with the potential to cause the worst impacts on the environment, which is a very conservative estimation.19 Consequently, experimental approaches using living organisms are likely more representative of the wastes behavior in the environment. In this work, five biotests involving different representants of trophic/functional levels in aquatic ecosystems were selected to test eluates of GLD: the phytotoxicity test with Lepidium sativum, the luminescence inhibition test with Aliivibrio fischeri, the growth inhibition test with Raphidocelis subcapitata, the growth inhibition test with Lemna minor, the immobilization test with Daphnia magna. Phytotoxicity tests are simple, replicable and rapid.31 Luminescence inhibition tests with Aliivibrio fischeri has been frequently proposed in test batteries to evaluate wastes ecotoxicity, as well as the growth inhibition test with Raphidocelis subcapitata. The growth inhibition test with Lemna minor was selected for this work to answer for the systemic route of chemical uptake additionally to the one through surface contact (single uptake route in Raphidocelis subcapitata). At last, the immobilization test with Daphnia magna is one of the most popular ecotoxicological tests, widely used and recommended for the HP 14 assessment. This study aimed at evaluating the ecotoxicity of GLD in order to classify it regarding the Hazard Property HP 14. The assessment was based not only on a comprehensive battery of biotests in the aquatic environment but also on the chemical composition of the waste. Thus, the comparison between these two approaches is an inherent secondary aim of the present study. Although other wastes have been studied regarding the dichotomy between prediction and assessment of ecotoxicity within the HP14 classification framework (see quoting above), to the best of our knowledge, this is the first time GLD ecotoxicological effects are assessed using such a holistic approach. Accordingly, this study presents valuable insights into the potential environmental impacts of a currently discarded waste produced widely by the pulp industry. Experimental Section (Materials and Methods) Materials GLD was supplied by a Kraft pulp mill from the central region of Portugal. In the laboratory, a sample of 5 kg was dried at room temperature, around 20 ºC, and then disintegrated in order to obtain a particle diameter 0.05), and most of the eluates resulted in negative inhibitions relatively to the control. These beneficial effects may have been caused by a favorable nutrient load for the bacteria. In fact, only the eluate at L/S 10 L/kg and natural pH seems to induce a mild (around 30%) inhibitory effect on bacteria luminescence. Indeed, this L/S ratio presented a higher EC (Supplementary Table A2), which may correspond to a larger amount of leached ions from GLD. The natural pH may have affected some organisms due to its high basic nature. Also, the bioavailability of certain metals decreases when pH correction towards lower levels is performed26 since pH influences the dissolution and precipitation of metals, as well as the speciation of inorganic species and sorption reactions.40 Consistently with our results, Stiernström et al.47 tested different eluate dilutions for L/S 10 L/kg of incineration bottom ash (IBA) from municipal solid waste (also an inorganic and basic waste), and following pH correction of the eluates to 8, they found no ecotoxic responses by A. fisheri. Ribé et al.48 tested different eluate concentrations for L/S 10 L/kg of matured IBA with pH 7.7 and also no ecotoxic effects were reported. 11 ACS Paragon Plus Environment


100 Luminescence inhibition (%)

Natural pH (30min) Corrected pH(30min)

80 60 40 20 0 -20 -40 -60

20 10

40

80

-80 160

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L/S ratio (L/kg)

Fig. 2 – Luminescence inhibition (mean ± standard error) of Aliivibrio fischeri exposed to eluates with different L/S ratios of GLD under natural and corrected pH. The long dashed line in grey indicates the median effect level.

Generally, the correction of pH seems to reduce the ecotoxic levels for L/S above 10 L/kg in the microalgae Raphidocelis subcapitata (Fig. 3). In fact, the L/S 10 L/kg extract is the one with a higher concentration of ions, presenting stronger buffering capacity. Speciation of metals and nutrients may be altered when the pH is corrected for values close to neutrality.49 Inhibition in yield above 50% was only found for eluates with natural pH at the L/S 20 L/kg (57% inhibition) and for eluates with pH correction at L/S 10 L/kg (60% inhibition). As for A. fischeri, it was not possible to fit a regression to the responses of R. subcapitata regardless of pH, thus the EC50 benchmarks could not be predicted. The negative yield inhibition values obtained for higher L/S represent higher microalgae growth compared to control treatments, which may be due to a supplementary amount of nutrients advantageous for this organism, consistently with the patterns found for A. fischeri. Stiernström et al.47 also tested IBA with R. subcapitata and no toxic response was found in this case either.


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Natural pH Corrected pH

100 Inhibition in yield (%)

50 0 -50 -100

40 20 10

80

160

-150 320

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


L/S ratio (L/kg)

Fig. 3 - Inhibition in yield (mean ± standard error) of Raphidocelis subcapitata as a function of different L/S ratios of GLD eluates with natural and corrected pH. The long dashed line in grey indicates the median effect level.

Fig. 4 displays the results (based on frond number and dry weight) for the growth inhibition test with Lemna minor. Eluates with natural pH caused remarkable frond yield inhibition, above 71%, representing high levels of ecotoxicity. Furthermore, strong chlorosis was observed with decreasing L/S ratio, which may be due to the increasing presence of leached toxic substances. The inhibition in yield was less prominent as eluates corrected for pH were tested; still, only the L/S 320 L/kg (highly conservative to represent GLD environmental behavior; see above) caused an inhibition below 50% (45%) and strong chlorosis was also observed with decreasing L/S ratio. Whereas the consistently high inhibitions through the eluate concentration range at natural pH did not allow the fitting of a feasible regression model, the EC50 estimated for corrected eluates was high suggesting a hazardous potential of GLD even following pH amendment. The frond number was more sensitive than dry weight, especially considering eluates corrected for pH but the responses of both endpoints were consistent in denoting a high hazardous potential of GLD following increased growth inhibition with increasing leached compounds from GLD to the eluates. Although showing similar trends, L. minor was more sensitive than the microalgae R. subcapitata, which is likely due to an additional uptake route (systemic) to surface contact.


120

EC50 = 246.31 (212.77-293.36) L/kg

40

160

0

40 20 10

20

80

Natural pH Corrected pH Fitting (R2) = 0,9842

EC50= 108.11 (85.47-146.84) L/kg

60 40 20 0

40 20 10

60

80

80

80

Natural pH Corrected pH Fitting (R2) = 0,9510

100

160

100

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B

320

A Inhibition in yield (dry weight) (%)

120

320

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Inhibition in yield (frond number) (%)


L/S ratio (L/kg)

L/S ratio (L/kg)

Fig. 4 - Mean ± standard error inhibition in yield based on frond number (A) and based on dry mass (B) of Lemna minor following exposure to eluates with different L/S ratios of GLD, with natural and corrected pH. The grey long-dash line indicates the median effect level, and the full lines represent the fitted logistic concentrationresponse models, the estimated EC50 values and corresponding 95% confidence intervals (within brackets) being presented in these cases.

Remarkable Daphnia magna immobilization (95-100%) was found for GLD with natural pH at L/S ratios within 10-80 L/kg (Fig. 5). This is likely linked to the pH effect given that the pH of these eluates is above 10 (Supplementary Table A2), exceeding the optimal testing conditions (pH 6-9; OECD guideline 202, 2004). It seems that pH adjustment has a positive effect regarding the immobilization parameter, but not enough to reverse the response to the two lowest L/S where 100% immobilization was still recorded. Note that the high buffering capacity of GLD requires a high acid quantity for pH decreasing and either the acid itself or recovery of initial pH levels may have led to such noxious effects. The estimated EC50 values for pH-amended and non-amended eluates consistently support the higher hazardous potential of the latter (higher EC50, i.e higher L/S and lower GLD content in the eluate). It is worth clarifying that these EC50 values should be considered carefully given that, although they are coherent with the experimental response profiles, the model distributions assumed for the estimation did not significantly reflect the experimental data (Goodness-of-fit Chi-square; p 320 L/kg E

A. fischeri

< 10 L/kg

NE

< 10 L/kg

NE

R. subcapitata

ND (1)

ND

ND (2)

ND

Frond number

> 320 L/kg

E

246.31 (212.77–293.36) E

Dry weight

108.11 (85.47–146.84)

E

ND (3)

ND

35.95 (28.35-45.34)

E

L. minor D. magna

130.18 (105.90-157.46) E

E: Ecotoxic in respect to the organism; NE: Not Ecotoxic in respect to the organism; ND: Not determined (not possible to estimate EC50 based on the dose-response curve). (1)

Yield inhibition (L/S 10 L/kg) = 49 %; (2) Yield inhibition (L/S 10 L/kg) = 60 %; (3) Yield inhibition (L/S 10 L/kg) = 59 %.

Conclusions The methodology of this work seems to be suitable for HP 14 assessment, providing enlightening results. The selected battery of biotests presented a clear picture of the hazardous potential of GLD towards aquatic ecosystems. The chemical analysis performed through ClassifyMyWasteTM software resulted in “Possible Hazard” regarding HP 14 for the sample of this study, and also for other simulations considering data from the literature. The biological analysis showed high GLD toxicity for 3 out of 5 organisms, and Lepidium sativum, Lemna minor and Daphnia magna were the most sensitive. The estimated EC50 values reflect high L/S ratios, reinforcing that low waste amounts in contact with water may induce deleterious effects in aquatic ecosystems. The pH correction of eluates was largely ineffective in decreasing GLD toxicity, suggesting that pH amendment may not be an adequate solution to prevent noxious environmental effects of this waste. Differential sensitivity to GLD was observed within the biotest battery, reinforcing the need to comprise different trophic and functional levels as well as the need to consider different chemical uptake routes when assembling a battery of ecotoxicological tests to assess wastes. Overall, the results of the current ecotoxicological testing suggest that GLD should be classified as ecotoxic (HP 14), which means potentially environmentally hazardous. This study reinforces that a battery of biotests is fundamental to a better understanding of the behavior of wastes in the environment and that these results should prevail over results from chemical analysis for ecotoxicity (HP 14) assessment. For this reason, recommendations on the biotest batteries, the methods to prepare eluate and criteria for interpretation and establishment of hazardous levels integrating chemical and ecotoxicological information should be a matter of attention in the near future at the regulatory level for a proper waste classification sensu 16 ACS Paragon Plus Environment

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HP14. Future scientific research is also needed to better support the update of the HP14 regulatory framework, mostly regarding the definition of the most appropriate testing approaches (e.g. test organisms and endpoints, test methods and test matrices) for groups of similar wastes, accounting to relative sensitivity and resolution. These studies should take into account the feasibility of the overall testing approach, balancing between ecological realism leading to better knowledge on multilevel environmental effects of wastes and the pace at which these wastes are produced and require an assessment before decisions on disposal routes. Conflicts of interest There are no conflicts to declare. Acknowledgements Thanks are due to the Strategic Projects of CIEQPF and CESAM (UID/QUE/00102/2013 and UID/AMB/50017/2019, respectively), financed by FCT/MEC through national funds. L.A. Gomes acknowledges Federal Institute of Education, Science, and Technology of Brasília IFB, Campus Ceilândia, for authorizing his PhD studies. J.L. Pereira is funded by national funds (OE) through FCT (art. 23 in DL 57/2016, changed by Law 57/2017). This work was developed under the project “Dry2Value, POCI-01-0247-FEDER-033662”, consortium with HRV and LenaAmbiente,

Funded

by

FEDER

-

Programa

Operacional

Competitividade

e

Internacionalização. This article was presented at the 13th International Chemical and Biological Engineering Conference (CHEMPOR 2018). The authors acknowledge the Scientific and Organizing Committees of the Conference for the opportunity to present this work. Supporting information Tables: Phytotoxicity classification categories; pH and electrical conductivity of tested eluates; electrical conductivity of osmotically adjusted test eluates for A. fischeri. References (1) Cabral, F., Ribeiro, H.M., Hilário, L., Machado, L., Vasconcelos, E. (2008). Use of pulp mill inorganic wastes as alternative liming materials. Bioresource Technology, 99: 8294–8298. (2) Monte, M.C., Fuente, E., Blanco, A., Negro, C. (2009). Waste management from pulp and paper production in the European Union. Waste Management, 29: 293-308.



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Graphical abstract

Synopsis Ecotoxicological assessment of a waste based on chemical composition and biotests is described to right classification and avoid loss of resources in landfills.


Characterization of Ecotoxicological Effects of Green Liquor Dregs

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