Discussion
Our study was designed to determine if non-industrial, mainly residential wood ash (NIWA) has the potential to be used as a forest soil amendment in central Ontario and be part of the solution to the widespread environmental Ca decline problem in central Ontario lakes and forests (
Watmough and Dillon 2003a,
2003b;
Jeziorski et al. 2008). To date, this NIWA source has neither been considered as a large-scale forest soil additive, nor as an aid to reverse widespread Ca decline in lakes, likely because of its unknown chemistry and distributed production. We do not think the latter reason should impede its consideration. After all, distributed production has not stopped any other residential recycling initiative.
To examine the question of whether NIWA could be part of the solution to Muskoka’s environmental Ca decline, we must: (i) document the concentration and solubility of Ca in the ash as part of the site-specific calculation of required application rates; (ii) compare levels of potentially toxic metals with regulated targets; (iii) if possible, quantify the actual toxicity of the wood ash to terrestrial and aquatic model species; (iv) quantify levels of any non-metallic ash components (organics and P) that might also pose environmental issues; (v) document quantities of NIWA that are produced annually in the region, and would likely be made available for the recycling programme; (vi) test the dosage calculations and ecotoxicological implications of NIWA issues in pilot studies, perhaps using an adaptive management philosophy; and (vii) resolve any major policy, logistical, economic, and stakeholder questions and impediments related to ash collection and post-collection treatment, e.g., pelletization, storage, delivery, distribution, and application. We have largely focused on the first five of these requirements in this paper. We recognize that the last two issues, particularly the last one, are major, so we do consider them briefly in the terminus of our Discussion.
However, to eliminate any confusion in the Discussion, we should briefly consider the goals of such a residential wood ash recycling programme. We suggest its central goals should be to: (i) increase citizen participation in environmental stewardship; (ii) increase the diversion of waste from landfill sites; (iii) reverse decades of Ca loss from watershed soils, thus increasing carbon capture and health of forests in eastern Canada; and (iv) indirectly, solve the widespread Ca loss problem in lakes by restoring soil base cation pools.
Our NIWA samples averaged 30% Ca and could replace missing Ca levels in forest soils. Such high levels of Ca are in agreement with those reported for wood-derived boiler ash: 3.6%–96.6% (as reviewed by
Vance 1996), 13.2%–27% (
Naylor and Schmidt 1986), 11.9%–28.4% (
Steenari and Lindqvist 1997), and 9.2%–24.79% (
AshNet 2018). Our results confirm Ca levels observed in ash from a home wood stove: 28.1%–32.1% (
Naylor and Schmidt 1986). Although our focus was on hardwood NIWA, we had an additional source of ash from a resident that burned exclusively wood pellets made from northern pine and spruce trees. This sample had a higher Ca concentration of 37% (
Azan 2018), but we would need additional samples to confirm that wood pellet stoves routinely produce ash with such high Ca levels.
Although our NIWA samples contained high total levels of Ca, it was not particularly soluble. Ca was released into aqueous media slowly from our hardwood NIWA, especially in the first 9 d of exposure (
Fig. 3). However, by day 30 of the solubility experiment, 0.4% of the total Ca was in solution, reaching an average of ~11 mg/L of Ca, still lower than the 15 mg/L we might have expected from the known solubility of CaCO
3, the primary Ca compound found in wood ash (
Steenari and Lindqvist 1997;
Serafimova et al. 2011). Such gradual solubility suggests that hardwood NIWA could be useful in the long term as a slow-release source of Ca for Muskoka forests, and potentially for low Ca lakes should wood ash be leached to them.
Our results suggest that heavy metal concentrations in NIWA should not prevent its use as a forest soil additive. None of the samples exceeded the CM2 standard, which would prevent use. Indeed, the majority of trace metal concentrations in the NIWA fell below the regulated levels for CM1, the target for unrestricted use (
Table 1). The exceptions were Cu and Zn, whose averages were just above the CM1 targets but well below the CM2 standard. The peak value we might expect to see in only 2.5% of NIWA samples also exceeded the CM1 target for Cu and Zn, as expected, given their means, but also for Cd. Such elevated levels of Cu and Zn, and on occasion Cd, likely reflect the unusually high metal deposition rates that occurred over the past 50 years or so (
Pratte et al. 2013) that are now reflected in forest soils (
Landre et al. 2010;
Watmough 2010;
Doucet et al. 2012) and lake sediments (
Couillard et al. 2008;
Landre et al. 2010). Any wood being burned now likely came from the same time period. As atmospheric metal deposition rates peaked several decades ago and are in decline, metal concentrations in NIWA will likely be lower in the future. Although it is unlikely that these rare individual samples would render bulk NIWA unusable, further metal analyses would certainly be required on bulk ash mixtures, as they are recycled for compost.
It is noteworthy that mean metal concentrations in our NIWA tended to be much lower than the mean and minimum values for industrial sources of wood ash (
Table 2), with the exception of Cu and Zn. These results suggest that NIWA would be no more of a toxic threat, if any, than many industrial sources of ash as an additive to forest soils in central Ontario. Hence, we do not think that the use of hardwood NIWA would result in metal toxicity in the receiving soil.
We provide the first direct assessment of the potential short- and longer-term toxicity of aqueous extracts of NIWA to
Daphnia. Although we did detect acute toxicity in concentrates, this completely disappeared with modest dilution, and we detected no toxicity of sedimented NIWA on
Daphnia survival, maturation, or brood production. Still, the high mortality in the concentrate and DF10 treatments must be explained. Beyond the strength of the concentrate itself (a 10% ash solution), we hypothesized this mortality had one of two logical sources: (
i) the high pH of the solutions, or (
ii) the concentration of elements present in the NIWA, including both metals and cations, other than Ca. The pH of the concentrates ranged from 10.65 to 12.49. To determine if the high pH of the concentrate and DF10 treatments explained the observed mortality rates, we repeated the 48 h experiment after first lowering the pH to 8, a pH typical of hard water lakes. As in the initial 48 h experiment without the pH adjustments, we detected 100% mortality rates in the concentrate and DF10 treatments, but excellent survival in the DF100 and DF1000 treatments (
Table S1). We concluded that high pH was not the cause of the mortality observed in
Daphnia neonates.
Our alternate hypothesis was that some other element (or elements) present in the NIWA extract was responsible for the observed mortality in the concentrate and DF10 treatments. We do not think that Cu or Zn were the responsible toxicants, because at the high pH of the medium, very little, if any, Cu or Zn would have been soluble (
Dortwegt and Maughan 2001;
Jarvis et al. 2012). The most logical possibility was K, which was very soluble in our NIWA (
Fig. 3). K levels in the concentrate and DF10 treatments ranged, respectively, from 2699 to 7871 mg/L, and 296 to 449 mg/L, much higher than the acute LC50 of 93 mg/L measured by
Biesinger and Christensen (1972). To check K toxicity to our daphniid clone in our soft water medium, we ran a 48 h bioassay using potassium chloride (KCl) at K concentrations of 50, 100, 150, 200, and 250 mg/L. We observed 100% survival in the first three concentrations (50, 100, and 150 mg/L), then 80% and 0% survival in the final two concentrations, i.e., at 200 and 250 mg/L of K, respectively (
Table S2). Interpolation of the survival (%) versus K concentration data provided an acute LC50 for K for our daphniid clone of between 200 and 250 mg/L, slightly higher than
Biesinger and Christensen’s (1972) value. This amount of variation in LC50s for metals is well known in inter-laboratory studies using
Daphnia (
Baird et al. 1990). These results strongly support the hypothesis that enough K was solubilized from the NIWA to account for the mortalities observed in the concentrate and DF10 treatments in the acute bioassays.
Daphnia neonates exposed to high levels of K concentrations (ranging from 195.5 to 1560 mg/L) would experience a depressed heart rate, and eventually death (
Baylor 1942). However, we do not expect such K toxicity from NIWA applications in nature, given ash dilution over time and distance. All required elements can exist at sub-optimal, optimal, and toxic levels, and it was our extreme concentrate (a 10% ash solution) that produced toxic levels in our assays. Still, as a precaution, K levels in ground and surface waters should be tracked shortly after NIWA additions, especially following precipitation events. We do know that the NIWA contains a lot of soluble K (
Fig. 3). Further, if spread, the NIWA should be dispersed widely, not left in concentrated piles, which might produce localized toxic levels of K after rain storms.
In addition to Ca and K, concentrations of other nutrients varied across the 10 hardwood NIWA samples. This result was expected as the chemical composition of wood ash can vary among tree species used as fuel, with the parts of tree in the fuel (e.g., bark, twigs, wood, and leaves), with the chemistry of the soil that supported the trees, with combustion temperature and type, and with storage of fuel wood (as reviewed by
Vance 1996;
Demeyer et al. 2001;
Pitman 2006). In central Ontario, local residents and the wood-fired pizza bakery burn the main stem or trunk of trees, bark, or branches (in descending order) of hardwood tree species (e.g., maple, oak, and beech) as a heating source (
Azan 2017), which might account for the variation in nutrients observed across the 10 hardwood samples collected. This is consistent with observations by
Pitman (2006), who also highlighted the variability in nutrient concentrations in ash that resulted from burning different tree species and tree parts. Sample 9 came from a wood-fired pizza bakery, and its higher levels for K, Mg, Na, and P could be due to the dosing of pizza bases with flour as they were placed in the oven. It is worth noting that flour has high concentrations of K (4%), P (13%), and Mg (7%) compared with the bole wood of trees.
Wood ash can have high P concentrations, and we could not recommend the large-scale addition of NIWA to the forest as a treatment for Ca decline if it would lead to the eutrophication of downstream waters. However, we feel this risk is low. P was the least soluble of the elements, at only 0.02% after 30 d for ash obtained from residences, and 0.05% for ash from the pizza bakery (Sample 9). From the dry ash analysis, we noted that Sample 9 contained 1.2% of P, about twice the 0.6% P average from the other nine sources of NIWA, all of which were residential (
Fig. 2). To explore the possibility that P in NIWA might pose a risk of eutrophication, we estimated the amount of readily available P that would be supplied to a watershed receiving 4 tonnes of NIWA/ha of watershed—a suggested minimum application rate that could be used to help solve the Ca decline problem in Muskoka (C. Reid, personal communication, 2017). At 4 tonnes/ha, ~800 g (0.8 kg) of P/ha (Appendix 2:
Azan 2018)—would be readily available to watershed soils. This value is roughly equivalent to the natural load of P from rain and snow of 750 g (0.75 kg)/ha, recorded annually in Muskoka (
Nicholls and Cox 1978), and is 16 times and three times more, respectively, than is normally released annually from forested areas in Muskoka (50 g/ha:
Dillon and Rigler 1975), and from the average stream exports of six soft water lakes in south-central Ontario (231 g/ha;
Eimers et al. 2018). As a precaution, changes in TP concentrations in ground and surface waters should be tracked post-addition of NIWA in watershed soils.
We do not think enough NIWA is generated in Muskoka to solve the Ca decline problem in local forests and lakes, given its widespread nature, but enough ash is generated in Ontario. Muskoka residents generate about 235 000 kg (235 tonnes) of NIWA per heating season. If the estimated net loss of Ca from the soil exchangeable pool is 7.14 kg/ha per year (
Watmough and Dillon 2003a), then the amount of Ca lost over the past 50 years of acid deposition is roughly 360 kg/ha or 0.36 tonnes/ha. If all the Ca in wood ash was soluble, this would require about a tonne of wood ash/ha. Assuming 4 tonnes/ha would be appropriate, Muskoka’s 235 tonnes of annual ash would treat only 58 ha, enough for a large plot-scale study, but not enough to solve the problem given its widespread nature (
Reid and Watmough 2016). However, about 18 000 tonnes of residential wood ash are generated in Ontario annually (
Azan 2017). In principle, this is enough to treat 4500 ha of Muskoka forests per year that certainly begins to address the scope of the problem over a decade or two. This suggests a province-wide NIWA recycling programme is worth considering as an option to solve the Ca decline problem in central Ontario. Of course, the inclusion of industrial sources of wood ash could shorten the time required to solve the problem.
Approved wood ash dosage rates have not been set for forest soils across Canada, and most provinces determine recommended doses based on the liming requirement of the soil and (or) on the trace metal levels in the ash and receiving soil (as reviewed by
Hannam et al. 2016). In Europe, approved doses range from 0.5 to 7.5 tonnes/ha, some of which are based on the quantity of Cd or P in the soil, the site (e.g., mixed peatland or upland forests), and soil type (e.g., nutrient poor sandy soils) (as reviewed by
Hannam et al. 2016). Field trials currently underway by participants in Canada’s national wood ash research network, AshNet (
nrcan.gc.ca/forests/researchcentres/glfc/ashnet/20279)—whose primary focus is forest productivity—are using similar dosage rates for industrial ash as used in Europe (ranging from 0.5 to 20 tonnes/ha;
Hannam et al. 2018). However, there is currently no understanding of what wood ash application rates to forested watersheds are needed to raise Ca concentrations in downstream waters to >1.5 mg Ca/L—a biological threshold above which
Daphnia reproduction and survival increases (
Ashforth and Yan 2008). As we expect Ca concentrations in many central Ontario lakes to fall to 1 mg/L or less (
Reid and Watmough 2016), there is clearly work to be done.
Although we have shown that, like industrial wood ash, NIWA can be used as a forest soil additive and, in consequence, benefit Muskoka forests and lakes, there are several barriers that prevent its wide-scale use as a forest soil additive in Canada. In their recent review,
Hannam et al. (2018) indicated that regulatory approval, the variability of wood ash chemistry, and a lack of knowledge of the effects of wood ash on forested sites are just some of the issues to overcome. The variability of NIWA is unlikely to be an issue, as metal concentrations are often lower than industrial sources and ash from treated or salt-laden wood are unlikely to be used. Current AshNet field trials are likely to provide useful knowledge on the effects of industrial wood ash on forested sites, which might be of use for choosing dosage rates that would provide surplus Ca that could increase levels in ground and thus surface waters.
Implementation of any wood ash recycling programme to help solve the Ca decline problem would have to address issues such as ash collection, ash distribution to forested areas (e.g., manual vs. mechanical, or aerial spreaders), dosage rates, ash storage, frequency, and methods of application. Resolving these issues can help to save money by increasing waste diversion from to municipal landfills (
Hope et al. 2017) and benefit the environment. With the exception of dosage rates, these are largely not ecotoxicological issues, but economic, logistical and engineering issues, and quite daunting ones at that. Once the ecotoxicological issues are resolved, they will require lots of enlightened discussion with waste management authorities and contractors if we are to develop a residential wood ash recycling programme to help solve the environmental problem of Ca decline.