A small number of viable options are presently available for the bleaching of wood pulp (delignification and brightening) during the manufacture of pulp and paper. The use of chlorine dioxide (ClO2) in the bleaching process has largely superceded the earlier use of Cl2, or elemental chlorine, in the majority of North American pulp mills: It was discovered over a decade ago that the previous widespread use of Cl2 contributed to the production and subsequent release to the environment of specific forms of potentially deleterious and highly persistent chlorinated organic contaminants, such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans.
The environmental risks and benefits associated with the virtual elimination of Cl2 in pulp and paper manufacture, and substitution during bleaching with ClO2 have been formally examined by many scientists; see for example papers by Axegård et al.(1993), Berry et al.(1991), Carey et al.(1993), Luthe et al.(1992), Munkittrick et al.(1996), Södergren (1989), Solomon et al.(1993), and Tana and Lehtinien (1996). In particular, Solomon et al.(1993) conducted a review and risk assessment of the chemistry and biological impacts associated with a 70% to 100% substitution of elemental chlorine with ClO2 at the request of the Alliance of Environmental Technologies.
Major conclusions from that review are as follows:
In the same review (Solomon et al.,1993), a number of areas of uncertainty based on the state of knowledge up to 1993 were also identified. In particular, it was concluded that -
Following completion of the 1993 review (Solomon et al.,1993), some interest groups have expressed the concern that replacement of Cl2 by ClO2 in the bleaching of pulp -- while responsible for a reduction in the production rate of organochlorine byproducts -- has not curtailed their production completely. Nor, according to some, can bioaccumulation of organochlorines from effluent for pulp mills using 100% ClO2 substitution be ruled out. One of the major points of contention between the most polarized of the factions is whether 100% ClO2 substitution has resulted in "only marginal environmental improvements", or whether such substitution is sufficient, and when coupled with effective secondary treatment of effluent represents an example of the "best available technology" for pulp and paper production.
Four years have elapsed since the 1993 review -- a period in which the actual monitoring data for pulp mills employing 100% ClO2 substitution has more than doubled. Considerable additional research has been completed on the fate and effects of pulp and paper mill effluent. This review builds on the content of the previous report (Solomon et al.,1993). It critically evaluates the previous conclusions, and addresses the key questions above along with other issues that have recently been identified as of potential importance. Like the previous review, this report is focused on the effects of pulp mill effluents in the aquatic ecosystem (including possible effects on wildlife via bioaccumulation through the food chain). It specifically excludes air emissions and other environmental impacts external to the mill, such as those associated with production of wood and the impacts of products exported from the mill.
Inherent within an assessment of the possible environmental risks associated with pulp and paper operations that utilize 100% ClO2 substitution during bleaching are two separate questions:
Both questions are directly relevant to understanding the larger environmental consequences of pulp and paper mill aqueous discharges; however, the second question is the one which is most directly relevant to risk management efforts centered around environmentally persistent organochlorines. We have attempted to address both questions here, and have endeavored to distinguish between the two issues.
It is also possible, although often more difficult, to compare the relative environmental risks of two or more operating practices. For example, implicit within an assessment of the risk of 100% ClO2 substitution for Cl2 is an assessment of the relative risks of bleaching using elemental chlorine versus chlorine dioxide. It is important to note that this document is not intended to provide a relative comparison between the risks associated with broadly different pulp and paper practices, such as the use of 100% ClO2 substitution during bleaching (commonly referred to as "elemental chlorine free", or ECF bleaching) versus totally chlorine free, or TCF bleaching.
A number of regulatory jurisdictions have begun to implement environmental risk assessment processes based on set frameworks. Environment Canada has developed a framework similar to that used in the U.S. Environmental Protection Agency (U.S. EPA, 1992) and illustrated in Figure 1 (Environment Canada, 1996). This framework was used as the basis for our assessment.
This process involves the following:
The Framework for risk assessment in the Canadian Environmental Protection Act (CEPA) explicitly recognizes that organisms resident in areas where background concentrations of naturally occurring substances are elevated are likely to be more tolerant to those substances (Environment Canada, 1997). This must be taken into consideration in the risk assessment process. This is particularly important in the risk assessment of substances found in pulp mill effluent and applies to both the naturally occurring substances and chlorinated and other substances produced during bleaching and other processes. Therefore in this assessment, we have also considered the presence of naturally occurring chlorinated and other substances.
As a prerequisite to estimating the risk associated with any input to the environment, one must understand both the major compounds involved (Chapter 2), and the immediate and long-term fate of those compounds. Constituents of pulp mill effluent may be placed in one or more of a small number of categories according to their molecular and, hence, environmental properties. The categorization is, in turn, useful for devising broad predictions regarding the possible extent and mechanism of effects in living organisms (see Chapter 4).
Ecological risk assessment involves estimating the concentration of potentially deleterious substances (i.e., the exposure) experienced by specific biological populations. This concentration is either measured directly, or estimated from amounts of input from a known source and subsequent redistribution between various environmental compartments. The exposure may then be compared with previously demonstrated exposure-response relationships leading to some toxicological endpoint. Overall, the risk to a population associated with pulp mill effluents will vary according to four factors:
There has been considerable progress since 1993 in characterizing more completely ClO2-bleaching effluent compounds (Chapter 2). It is also possible to predict, with a quantifiable degree of certainty, the environmental redistribution from physicochemical and environmental properties (e.g., through fugacity-type or other partitioning models). There is, however, insufficient knowledge of concentration-response relationships at the sub-organismic, population, community or ecosystem level (see Chapters 4 and 5) for some of the recently elucidated compounds. It is clear that recent research on biological effects of treated pulp mill effluent has undergone a switch in emphasis with regard to contaminants of concern, to compounds more directly associated with the pulping as opposed to bleaching process. Some of the contaminants of concern are also natural plant products, or may be produced naturally in the aquatic environment