Article pubs.acs.org/est
The Relationship between Organic Loading and Effects on Fish Reproduction for Pulp Mill Effluents across Canada Pierre H. Martel,*,† Brian I. O’Connor,† Tibor G. Kovacs,† Michael R. van den Heuvel,‡ Joanne L. Parrott,§ Mark E. McMaster,§ Deborah L. MacLatchy,∥ Glen J. Van Der Kraak,⊥ and L. Mark Hewitt§ †
FPInnovations, 570 boul. Saint-Jean, Pointe-Claire, QC Canada, H9R 3J9 Canadian Rivers Institute, Department of Biology, University of Prince Edward Island, 550 University Avenue, Charlottetown, PEI Canada, C1A 4P3 § Water Science and Technology Directorate, Environment and Climate Change Canada, 867 Lakeshore Road, Burlington, ON Canada, L7S 1A1 ∥ Canadian Rivers Institute, Department of Biology, Wilfrid Laurier University, 75 University Avenue West, Waterloo, ON Canada, N2L 3C5 ⊥ Department of Integrative Biology, University of Guelph, 50 Stone Road East, Guelph, ON Canada, N1G 2W1 ‡
S Supporting Information *
ABSTRACT: This study builds upon the work of a multiagency consortium tasked with determining cost-effective solutions for the effects of pulp mill effluents on fish reproduction. A laboratory fathead minnow egg production test and chemical characterization tools were used to benchmark 81 effluents from 20 mills across Canada, representing the major pulping, bleaching, and effluent treatment technologies. For Kraft and mechanical pulp mills, effluents containing less than 20 mg/L BOD5 were found to have the greatest probability of having no effects. Organic loading, expressed as the total detected solvent-extractable components by gas chromatography/mass spectrometry (GC/ MS), also correlated with decreased egg laying. Exceptions were found for specific Kraft, mechanical, and sulfite mills, suggesting yet unidentified causative agents are involved. Recycled fiber mill effluents, tested for the first time, were found to have little potential for reproductive effects despite large variations in BOD5 and GC/MS profiles. Effluent treatment systems across all production types were generally efficient, achieving a combined 82−98% BOD5 removal. Further reductions of final effluent organic loadings toward the target of less than 20 mg/L are recommended and can be realized through biotreatment optimization, the reduction of organic losses associated with production upsets and selecting best available technologies that reduce organic loadings to biotreatment.
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the effects of mill effluents on fish in their receiving environments for mill operators has been lacking. The first cycles of the Canadian Environmental Effects Monitoring (EEM) program identified two main environmental issues related to pulp mill effluents.6 In the case of benthic invertebrates, the evidence pointed to nutrient enrichment, as invertebrate abundance was increased in pulp mill receiving areas. In the case of fishes, a national assessment of the data also found evidence that nutrient enrichment was related to increased indices of greater energy storage and liver somatic indices of effluent-exposed fishes. This, however, was also
INTRODUCTION The effects of pulp and paper mill effluents on fish reproduction has been well documented since the the late 1980s. These include delayed sexual maturity, decreased gonad size, reduced gonadal and circulating sex steroids, and reduced secondary sex characteristics in wild fish. Effects have been reported from all pulp producing nations where investigations have been conducted, including Sweden, Finland, Canada, the United States, New Zealand, and Chile,1−3 encompassing a broad range of feedstocks, pulping processes, and effluent biotreatment systems. A large body of research has focused on the mechanisms of action on the endocrine system, determining the presence of effluent components functioning as estrogens, androgens,1 and more recently, chemicals interfering with the neuroendocrine system.4,5 Despite these efforts, progress toward the causes and potential solutions for © 2017 American Chemical Society
Received: Revised: Accepted: Published: 3499
November 25, 2016 February 3, 2017 February 21, 2017 February 21, 2017 DOI: 10.1021/acs.est.6b05572 Environ. Sci. Technol. 2017, 51, 3499−3507
3500
NSSC, OCC, recycle
S19
Mill 1: OEDEHH, E DE DH; Mill 2: hydrogen peroxide; Mill 3: none
none
none none
hydrogen peroxide/ sodium hydrosulfite sodium hydrosulfite
sodium hydrosulfite/ hydrogen peroxide sodium hydrosulfite sodium hydrosulfite
sodium hydrosulfite sodium hydrosulfite hydrogen peroxide
Line 1: ODEoDnD ODEopDnD ODnEopDnD; Line 2: OA(ZD) EDnD D0EopD1EpD2 D0EopHEp(H)D2
DEoDepD D0EopD1
OD0EopD1EpD2 Line 1: DNEPD; Line 2: DEPD
Line 1: none; Line 2: D0EopWpD1
100% purchased pulp 36−42% yellow birch, 18−21% poplar, 6−7% maple/beach, 30− 40% OCC Complex Mills Using Sulfite Pulping 30−38% birch, 14−20% maple, 7−16% poplar, 1−16% other HW, 35% OCC Mill 1: 8−64% spruce, 0−8% red pine, 32−84% gray pine; Mill 2: 100% maple; Mill 3: purchase pulp 60−80% SW, 20−40% HW
100% old papers/OCC
75% spruce, 13% fir, 7% red and white pine, 4% jack pine 100% black spruce Recycled Pulp, Paper, and Board Mills 100% old papers
BK pulp dissolving grade pulp
75% spruce, 25% pine 59−67% maple,25−35% aspen,0−15% birch Mechanical Mills 30% fir, 70% spruce 60% pine, 40% spruce Line 1: 50−75% aspen, 25% birch, 25% maple; Line 2: 66% fir/ spruce/other, 33% aspen TMP: 25−30% fir, 70−75% spruce; Deinked pulp: ≥ 80 ONP
Line 1: dissolving pulp; Line 2: BCTMP; Line 3: coated paperboard
1569
286
297 688
fine paper corrugated medium
corrugated medium
675
155
669 628
889
1385 657 726
591 471
985
1092 1465
756 1403
760
tissue
deinked pulp
newsprint newsprint
newsprint
newsprint newsprint BCTMP
BK pulp
Line 1: 70% jack pine, 30% spruce, ∼red/white pine; Line 2: birch/maple
BK pulp fine paper
BK pulp white top, coated, cups, plates
UGW and BK pulp
Kraft Mills Line 1: 50% spruce, 50% poplar; Line 2: 100% spruce 15% fir/larch, 50% pine, 35% spruce 11−29% broke, 0−11% sawdust, 0−26%; DLK: 22−43% birch/ poplar, 25−47% fir/spruce/white pine/red pine/larch 80% black spruce, 20% gray pine 0.5 mg/L. Curve fitting for GCIs suggest an IC50 of 0.17 mg/L with 95% confidence intervals between 0.03 and 0.31 mg/L. Four samples from mill K3 (4831, 4851, 4867, and 4908 in the Supporting Information, Table S1) contained significantly lower low BOD5 ( 0.05), past work strongly correlated egg production with organic losses associated with the black liquor recovery system and condensate handling.11 Therefore, any housekeeping or process conditions that either control or reduce the release of organics from these sources will be beneficial in terms of decreasing both the BOD5 loading and the level of causative agents entering the treatment system. Uncontrolled losses from black liquor recovery are also toxic to biomass within treatment systems, thus exacerbating BOD5 loadings.11 A useful reference document in this regard is the “Best Available Techniques (BAT)” report recently updated by the European Commission’s Institute for Prospective Technological Studies in 201418 (http://eippcb.jrc.ec.europa.eu/reference/BREF/PP_revised_ BREF_2015.pdf) that identifies areas of the process that could benefit from optimization to reduce organic losses. This study provides strategies for mills to maintain a minimal final effluent BOD5. Two outliers from mill K3 were evident, where low effluent BOD5 values (
