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I have installed SandboxLink extension that provides each user their own sandbox accessible through their personal menu bar (top right)
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Climate change affects both terrestrial<ref>Diffenbaugh, N. S. and Field, C. B., 2013. Changes in Ecologically Critical Terrestrial Climate Conditions. Science, 341(6145), pp. 486-492. [https://doi.org/10.1126/science.1237123 doi: 10.1126/science.1237123]</ref> and aquatic biomes<ref>Hoegh-Guldberg, O., and Bruno, J. F., 2010. The Impact of Climate Change on the World’s Marine Ecosystem. Science, 328(5985), pp. 1523-1528. [https://doi.org/10.1126/science.1189930 doi: 10.1126/science.1189930]</ref> causing significant effects on ecosystem functions and biodiversity<ref name=":0">Bellard, C., Berteslsmeier, C., Leadley, P., Thuiller, W., and Courchamp, F., 2012. Impacts of climate change on the future of biodiversity. Ecological Letters, 15(4), pp. 365-377. [https://doi.org/10.1111/j.1461-0248.2011.01736.x doi: 10.1111/j.1461-0248.2011.01736.x] [//www.enviro.wiki/images/a/a4/Bellard2012.pdf Article pdf]</ref>. Climate change is affecting several key ecological processes and patterns that will have cascading impacts on wildlife and habitat<ref name=":1">Inkley, D. B., Anderson, M. G., Blaustein, A. R., Burkett, V. R., Felzer, B., Griffith, B., Price, J., and Root, T. L., 2004. Global Climate Change and Wildlife in North America. Wildlife Society Technical Review 04-2. The Wildlife Society, Bethesda, MD, 26 pp. [//www.enviro.wiki/images/f/f1/Inkley2004.pdf Report pdf]</ref>. For example, sea-level rise, changes in the timing and duration of growing seasons, and changes in primary production are mainly driven by changes to global environmental variables (e.g., temperature and atmospheric CO<sub>2</sub>). Climate-induced changes in the environment ultimately impact wildlife population abundance and distributions.  
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<br />
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'''Munitions Constituents – Photolysis'''
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<div style="float:right;margin:0 0 2em 2em;">__TOC__</div>
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Munitions compounds (MCs), including [[wikipedia:TNT|2,4,6-trinitrotoluene]] (TNT), [[wikipedia:RDX|hexahydro-1,3,5-trinitro-1,3,5-triazine]] (RDX), [[wikipedia:2,4-Dinitroanisole|2,4-dinitroanisole]] (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), and [[wikipedia:Nitroguanidine|nitroguanidine]] (NQ), absorb light in the UV range and are therefore susceptible to photolysis on soil surfaces and in surface water. Photochemical reactions are important to consider when assessing the environmental impact of MCs since they can yield products that differ from their parent compounds in both toxicity and transport behavior. Quantum yield calculations can aid in predicting the photolysis rates and half-lives of MCs. The photolysis of MCs may be enhanced or inhibited in the presence of compounds that are also excited by UV irradiation. Munitions compounds (MCs), including 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), 2,4-dinitroanisole (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), and nitroguanidine (NQ), absorb light in the UV range and are therefore susceptible to photolysis on soil surfaces and in surface water. Photochemical reactions are important to consider when assessing the environmental impact of MCs since they can yield products that differ from their parent compounds in both toxicity and transport behavior. Quantum yield calculations can aid in predicting the photolysis rates and half-lives of MCs. The photolysis of MCs may be enhanced or inhibited in the presence of compounds that are also excited by UV irradiation.
 
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'''Related Article(s):'''
 
'''Related Article(s):'''
  
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*'''[[Munitions Constituents]]'''
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*[[Climate Change Primer|Climate Change]]
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*[[Predicting Species Responses to Climate Change with Population Models]]
  
  
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'''Contributor(s)''': Dr. Warren Kadoya
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'''Contributor(s):''' Dr. Breanna F. Powers and Dr. Julie A. Heath
  
  
 
'''Key Resource(s):'''
 
'''Key Resource(s):'''
  
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*Environmental Organic Chemistry, Chapter 15: Direct Photolysis<ref name=":1">Schwarzenbach, R.P., Gschwend, P.M., and  Imboden, D.M., 2002.  Chapter 15, Direct Photolysis. In: Schwarzenbach, R.P., Gschwend, P.M., and Imboden, D.M. (eds). Environmental Organic Chemistry. 2nd ed. Hoboken, NJ: John Wiley & Sons, Inc, pp. 611-654. [https://doi.org/10.1002/0471649643.ch15 doi:10.1002/0471649643.ch15]</ref>
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*Global climate change and wildlife in North America. Wildlife Society Technical Review 04-2<ref name=":1" />
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*[//www.enviro.wiki/images/6/64/ERDC2007.pdf Photochemical Degradation of Composition B and Its Components]<ref name=":2">Pennington, J.C., Thorn, K.A., Co, L.G., MacMillan, D.K., Yost, S., and Laubscher, R.D., 2007. Photochemical Degradation of Composition B and Its Components. U.S. Army Engineer Research and Development Center (ERDC)/ Environmental Laboratory (EL) [https://hdl.handle.net/11681/6837 TR-07-16]. [//www.enviro.wiki/images/6/64/ERDC2007.pdf Report]</ref>
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*Impacts of climate change on the future of biodiversity<ref name=":0" />
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*Verification of RDX Photolysis Mechanism<ref>Peyton, G.R., LeFaivre, M.H., and Maloney, S.W., 1999. Verification of RDX photolysis mechanism. U.S. Army Engineer Research and Development Center (ERDC)/ Construction Engineering Research Laboratory (CERL)
 
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[https://apps.dtic.mil/sti/citations/ADA371755 TR 99/93]. [//www.enviro.wiki/images/c/ca/ADA1999.pdf Report]</ref>
 
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*Photochemical transformation of the insensitive munitions compound 2,4-dinitroanisole<ref>Rao, B., Wang, W., Cai, Q., Anderson, T., and Gu, B., 2013. Photochemical Transformation of The Insensitive Munitions Compound 2,4-Dinitroanisole. Science of The Total Environment, 443, pp. 692-699. [https://doi.org/10.1016/j.scitotenv.2012.11.033 doi: 10.1016/j.scitotenv.2012.11.033]</ref>
 
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*Photo-transformation of aqueous nitroguanidine and 3-nitro-1,2,4-triazol-5-one: Emerging munitions compounds<ref>Becher, J.B., Beal, S.A., Taylor, S., Dontsova, K., Wilcox, D.E., 2019. Photo-transformation of aqueous nitroguanidine and 3-nitro-1,2,4-triazol-5-one: Emerging munitions compounds. Chemosphere, 228, pp. 418-426.  [https://doi.org/10.1016/j.chemosphere.2019.04.131 doi:10.1016/j.chemosphere.2019.04.131]</ref>
 
  
 
==Introduction==
 
==Introduction==
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[[wikipedia:Insensitive_munition|Insensitive munitions]], including [[wikipedia:IMX-101|IMX-101]] and IMX-104, are replacing traditional explosives because they are less prone to accidental detonation and therefore safer for military personnel to handle. [[wikipedia:IMX-101|IMX-101]], composed of [[wikipedia:2,4-Dinitroanisole|2,4-dinitroanisole]] (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), and [[wikipedia:Nitroguanidine|nitroguanidine]] (NQ), will replace [[wikipedia:TNT|2,4,6-trinitrotoluene]] (TNT) in artillery; IMX-104, composed of DNAN, NTO, and [[wikipedia:RDX|hexahydro-1,3,5-trinitro-1,3,5-triazine]] (RDX), will replace [[wikipedia:Composition_B|Composition B]] (Comp B) in mortars<ref>BAE Systems, 2021. [https://www.baesystems.com/en-us/feature/making-explosives-safer. Making explosives safer]</ref>. As both traditional munitions compounds and these insensitive munitions compounds (collectively referred to as MCs) may be deposited onto firing ranges via incomplete detonation, understanding their environmental fate is of concern<ref>Pennington, J.C., Silverblatt, B., Poe, K., Hayes, C.A., and Yost, S, 2008. Explosive residues from low-order detonations of heavy artillery and mortar rounds. Soil and Sediment Contamination: An International Journal, 17(5), pp. 533-546. [https://doi.org/10.1080/15320380802306669 doi: 10.1080/15320380802306669]</ref>. Phototransformation due to sunlight exposure is an important fate-controlling parameter for MCs and can occur on the surfaces of solid explosive particles, as shown in Figure 1, as well as in the aqueous phase following MC dissolution by rainwater. Furthermore, MC photolysis can be affected by the presence of natural organic matter and other compounds that are excited by sunlight.  
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[[File:PowersFig1.png|thumb|900px|left | Figure 1. The predicted extinction risk (by percentage with 95% CIs) from climate change by different regions, colors represent a gradient from least to most extinction risks (green to red) based upon the number of relevant studies (n). Figure is from Urban (2015)<ref name=":2" />. Reprinted with permission from AAAS. Any use of this figure requires the prior written permission of AAAS]]
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[[File: PhotolysisFig1.png | thumb | 650px | left | Figure 1. Color change over time as particles of IMX-101 and IMX-104 were exposed to sunlight and rainfall, suggesting phototransformation. Image courtesy of the U.S. Army Engineer Research and Development Center<ref>Dontsova, K., Taylor S., Pesce-Rodriguez, R., Brusseau, M., Arthur, J., Mark, N., Walsh, M., Lever, J.,   and Simunek, J., 2014. Dissolution of NTO, DNAN, and insensitive munitions formulations and their fates in soils. U.S. Army Engineer Research and Development Center (ERDC)/ Cold Region Research and Engineering Laboratory (CRREL) TR-14-23. [[Special:FilePath/ERDC2014.pdf| Report]]
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Global climate change will affect ecosystem functions and cycles such as nutrient, hydraulic, and carbon cycles, changing aspects of environmental conditions such as temperature, soil moisture, and precipitation<ref>Davidson, E. A. and Janssens, I. A., 2006. Temperature sensitivity of soil carbon decomposition and feedbacks to climate change. Nature, 440, pp. 165-173.[https://doi.org/10.1038/nature04514 doi: 10.1038/nature04514]</ref><ref>Melillo, J. M., McGuire, A. D., Kicklighter, D. W., Moore, B., Vorosmarty, C. J., and Schloss, A. L., 1993. Global climate change and terrestrial net primary production. Nature, 363, pp. 234-240. [https://doi.org/10.1038/363234a0 doi: 10.1038/363234a0]</ref>. Wildlife species are adapted to their environments and changes to the environment and habitat conditions will mediate effects, either directly or indirectly, on species survival, fecundity and ultimately population persistence<ref>Alig, R. J., Technical Coordinator, 2011. Effects of Climate Change on Natural Resources and Communities: A Compendium of Briefing Papers. U.S. Department of Agriculture, Forest Service, Pacific Northwest Research Station, General Technical Report, [https://www.fs.usda.gov/treesearch/pubs/37513 PNW-GTR-837], Portland, OR, 169p. [https://doi.org/10.2737/PNW-GTR-837 doi:10.2737/PNW-GTR-837] [//www.enviro.wiki/images/f/f2/Pnwgtr837.pdf Report pdf]</ref><ref>Acevedo-Whitehouse, K., and Duffus, A. L. J., 2009. Effects of environmental change on wildlife health. Philosophical Transactions of the Royal Society B: Biological Sciences, 364(1534), pp. 3429-3438. [https://doi.org/10.1098/rstb.2009.0128 doi: 10.1098/rstb.2009.0128]</ref><ref>Milligan, S. R., Holt, W. V., and Lloyd, R., 2009. Impacts of climate change and environmental factors on reproduction and development in wildlife. Philosophical Transactions of the Royal Society B: Biological Sciences, 364(1534), pp. 3313-3319. [https://doi.org/10.1098/rstb.2009.0175 doi: 10.1098/rstb.2009.0175] [//www.enviro.wiki/images/a/ad/Milligan2009.pdf Article pdf]</ref>. The ability to adapt to changing habitat conditions as a result of climate change will differ across individual species and between populations. Some wildlife species may be more vulnerable to climate change than other species (Figure 1). Vulnerability is often linked to particular life-history traits (e.g., specialized habitat needs or limited dispersal abilities, see Pacifici et al. 2015P<ref>Pacifici, M., Foden, W., and Visconti, P., 2015. Assessing species vulnerability to climate change. Nature Climate Change 5, pp. 215-225. [https://doi.org/10.1038/nclimate2448 doi: 10.1038/nclimate2448]</ref> for a review on species vulnerability to climate change) or genetic composition. For example, grassland birds may be more vulnerable to changing climate than forest birds as forests can buffer change more so than grasslands<ref>Jarzyna, M. A., Zuckerberg, B., Finley, A. O., and Porter, W. F., 2016. Synergistic effects of climate change and land cover: grassland birds are more vulnerable to climate change. Landscape Ecology, 31(10), pp. 2275-2290. [https://doi.org/10.1007/s10980-016-0399-1 doi: 10.1007/s10980-016-0399-1]</ref>. Projected changes in the climate will generally have adverse effects of wildlife populations<ref>IPCC, 2001. Climate Change 2001: Synthesis Report. A Contribution of Working Groups I, II, and III to the Third Assessment Report of the Intergovernmental Panel on Climate Change. R.T. Watson and the Core Writing Team (eds.). Cambridge University Press, Cambridge, United Kingdom, and New York, NY, USA, 398p. [//www.enviro.wiki/images/5/56/IPCC2001.pdf Report pdf]</ref>, though there are some species coping with climate change or benefitting from environmental change.  For example, American kestrels (Falco sparverius) have shifted their breeding phenology to earlier in the year and may now raise two broods of young within a breeding season<ref>Smith, S. H., Steenhof, K., McClure, C. J. W., and Heath, J. A. 2017. Earlier nesting by generalist predatory bird is associated with human responses to climate change. Journal of Animal Ecology, 86(1), pp. 98-107. [https://doi.org/10.1111/1365-2656.12604 doi: 10.1111/1365-2656.12604] [//www.enviro.wiki/images/5/5d/Smith2017.pdf Article pdf]</ref>.  
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</ref>.]]
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[[File:PowersFig2.png|thumb|900px|right| Figure 2. Conceptual diagram showing how increased water temperatures and pCO₂ (partial pressure of carbon dioxide) affect the early life stages of fish. Where arrow direction indicated increasing rate ( ↑ ), decreasing rate ( ↓ ), or both directions depending on other environmental variables ( ↕️ ).  Figure is from Pankhurst and Munday (2011)<ref name=":4" />.]]
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==The influence of climate change on wildlife and habitats==
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Climate change effects on wildlife include increases and changes in disease and pathogens distribution, patterns, and outbreaks in wildlife<ref>Bradley, B. A., Wilcove, D. S., and Oppenheimer, M., 2010. Climate change increases risk of plant invasion in the Eastern United States. Biological Invasions, 12, pp.1855-1872. [https://doi.org/10.1007/s10530-009-9597-y doi: 10.1007/s10530-009-9597-y]</ref><ref>Cudmore, T. J., Björklund, N., Carroll, A. L., and Lindgren, B. S., 2010. Climate change and the range expansion of an aggressive bark beetle: evidence of higher beetle reproduction in naïve host tree populations. Journal of Applied Ecology, 47(5), pp. 1036-1043. [https://doi.org/10.1111/j.1365-2664.2010.01848.x doi: 10.1111/j.1365-2664.2010.01848.x] [//www.enviro.wiki/images/b/b3/Cudmore2010.pdf Article pdf]</ref><ref>Price, S. J., Leung, W. T., Owen, C. J., Puschendorf, R., Sergeant, C., Cunningham, A. A., Balloux, F., Garner, T. W., and Nichols, R. A., 2019. Effects of historic and projected climate change on the range and impacts of an emerging wildlife disease. Global Change Biology, 25(8), pp. 2648-2660. [https://doi.org/10.1111/gcb.14651 doi: 10.1111/gcb.14651]</ref>; changes in range distributions and shifts in latitudinal and elevational gradients; changes in phenology or the timing of life cycle events that may create phenological mismatches<ref>Renner, S. S., and Zohner, C. M., 2018. Climate Change and Phenological Mismatch in Trophic Interactions Among Plants, Insects, and Vertebrates. Annual Review of Ecology, Evolution, and Systematics, 49, pp. 165-182. [https://doi.org/10.1146/annurev-ecolsys-110617-062535 doi: 10.1146/annurev-ecolsys-110617-062535]</ref>; and extinction or population reduction<ref name=":2">Urban, M. C., 2015. Accelerating extinction risk from climate change. Science, 348(6234), pp. 571-573. [https://doi.org/ 10.1126/science.aaa4984 doi: 10.1126/science.aaa4984] [//www.enviro.wiki/images/1/15/Urban2015.pdf Article pdf]</ref>. The effects of climate change across a species’ range will most likely not be homogenous, meaning it can vary substantially, especially if a species’ range spans across different continents as exhibited by many migratory birds. Other changes in habitat include shifting vegetation (i.e., tree-lines are shifting to higher elevations), changes in nutrients in plants, earlier snowmelt and run-off, increase in invasive species, warming of streams and rivers, reduction or degradation of habitat (i.e., glacial melt), and an increase in large wildfires<ref>Barbero, R., Abatzoglou, J. T., Larkin, N. K., Kolden, C. A., and Stocks, B., 2015. Climate change presents increased potential for very large fires in the contiguous United States. International Journal of Wildland Fire, 24(7), pp. 892-899. [https://doi.org/10.1071/WF150830128 doi: 10.1071/WF150830128] [//www.enviro.wiki/images/0/08/Barbero2015.pdf Article pdf]</ref>and droughts<ref>Schlaepfer, D. R., Bradford, J. B., Lauenroth, W. K., Munson, S. M., Tietjen, B., Hall, S. A., Wilson, S. D., Duniway, M. C., Jia, G., Pyke, D. A., Lkhagva, A., and Jamiyansharav, K., 2017. Climate change reduces extent of temperate drylands and intensifies drought in deep soils. Nature Communications, 8, pp. 14196. [https://doi.org/10.1038/ncomms14196 doi: 10.1038/ncomms14196]</ref>.
  
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==Direct photolysis==
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Although climate change effects on wildlife often are linked to species-specific traits, there are general impacts associated with taxonomic groups<ref name=":1" />. For fish it can affect reproduction<ref name=":4">Pankhurst, N. W., and Munday, P. L., 2011. Effects of climate change on fish reproduction and early life history stages. Marine and Freshwater Research, 62(9), pp. 1015-1026. [https://doi.org/10.1071/MF10269 doi: 10.1071/MF10269] [[Special:FilePath/Pankhurst2011.pdf| Article pdf]]</ref>, growth, and recruitment<ref name=":3">Lynch, A. J., Myers, B. J. E., Chu, C., Eby, L. A., Falke, J. A., Kovach, R. P., Krabbenhoft, T. J., Kwak, T. J., Lyons, J., Paukert, C. P., and Whitney, J. E., 2016. Climate Change Effects on North American Inland Fish Populations and Assemblages. Fisheries, 41(7), pp. 346-361. [https://doi.org/10.1080/03632415.2016.1186016 doi: 10.1080/03632415.2016.1186016]</ref>(Figure 2). Cold-water fish such as inland North American species are highly affected with the warming of streams and rivers<ref name=":3" />. Amphibians are highly sensitive to their environment and changes in temperature and moisture can affect development, range, abundance, and phenology<ref>Blaustein, A.R., Walls, S.C., Bancroft, B.A., Lawler, J.J., Searle, C.L., and Gervasi, S.S., 2010. Direct and Indirect Effects of Climate Change on Amphibian Populations. Diversity, 2(2), pp. 281-313.[https://doi.org/10.3390/d2020281 doi: 10.3390/d2020281] [[Media:Blaustein 2010.pdf | Article pdf]]</ref><ref name=":1" /><ref>Ficetola, G. F., and Maiorano, L., 2016. Contrasting effects of temperature and precipitation change on amphibian phenology, abundance and performance. Oecologia, 181(3), pp. 683-693. [https://doi.org/10.1007/s00442-016-3610-9 doi: 10.1007/s00442-016-3610-9]</ref>. In reptiles, climate change effects can alter thermoregulation patterns, affect female reproduction and in some species, change sex ratios with increasing temperature<ref name=":1" />. Furthermore, for many bird species the timing of migration and other phenological events are affected by climate change<ref>Crick, H. Q. P., 2004. The impact of climate change on birds. Ibis, 146(s1), pp. 48-56. [https://doi.org/10.1111/j.1474-919X.2004.00327.x doi: 10.1111/j.1474-919X.2004.00327.x] [//www.enviro.wiki/images/c/c9/Crick2004.pdf Article pdf]</ref>. Range shifts, growth size, and survival are linked to climate change for mammals<ref name=":1" />. Arctic marine mammals are closely linked to sea ice dynamics and a changing climate will affect these dynamics<ref>Kovacs, K. M., Lydersen, C., Overland, J. E., and Moore, S. E., 2011. Impacts of changing sea-ice conditions on Arctic marine mammals. Marine Biodiversity, 41, pp. 81-194. [https://doi.org/10.1007/s12526-010-0061-0 doi: 10.1007/s12526-010-0061-0]</ref>. Therefore, it is increasingly important for conservation and management plans to consider the effects of climate change on wildlife and habitat for the geographic location<ref>Mawdsley, J. R., O’Malley, R., and Ojima, D. S. 2009. A Review of Climate-Change Adaptations Strategies For Wildlife Management and Biodiversity Conservation. Conservation Biology, 23(5), pp. 1080-1089. [https://doi.org/10.1111/j.1523-1739.2009.01264.x doi: 10.1111/j.1523-1739.2009.01264.x]</ref>.
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Compounds that absorb [[wikipedia:Ultraviolet|ultraviolet]] (UV, 100-400 nm) and/or [[wikipedia:Visible_spectrum|visible]] (Vis, 400-800 nm) light can undergo direct photolysis from sunlight. Light is absorbed in discrete units, or [[wikipedia:Photon|photons]], and the energy of these photons is indirectly proportional to the wavelength of the light. When a chemical molecule absorbs a photon, its ground state electrons may become excited. As the excited electrons return to the ground state, they may undergo a chemical reaction that results in transformation. Figure 2 shows that the UV range is further divided into UV-A (315-400 nm), UV-B (280-315 nm), and UV-C (100-280 nm). Because most of UV-C is filtered out by the Earth’s atmosphere, direct photolysis of compounds at the surface primarily involves UV-A and UV-B<ref name=":0">Brennan, P., and Fedor, C., 1994. Sunlight, UV, & accelerated weathering. [https://www.q-lab.com/ Q-Lab Corporation], Technical Bulletin LU-0822. [[Special:FilePath/Brennan1994.pdf| Paper]]</ref>.
 
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[[File: PhotolysisFig2.png | thumb | 650px | left | Figure 2. The ultraviolet and visible spectrum of sunlight measured at noon in midsummer in Cleveland, Ohio in June 1986. Reproduced with permission from [https://www.q-lab.com/ Q-Lab Corporation]<ref name=":0" />.]]
 
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The MCs [[wikipedia:TNT|TNT]], [[wikipedia:RDX|RDX]], DNAN, NTO, and [[wikipedia:Nitroguanidine|NQ]] may undergo direct photolysis since they all absorb light in the UV-Vis range (Figure 3). These graphs convey the probability that the compounds will absorb light at a given wavelength. The absorption maxima correspond to one or more electrons transitioning to an excited state.
 
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[[File: PhotolysisFig3.png | thumb | 650px | left | Figure 3. UV-Vis absorbance spectra for munitions compounds. Spectra over the wavelength range of 200-800 nm were obtained using a Jasco V-630 UV-Vis Spectrophotometer and quartz cuvettes, UV transparent to 200 nm (YeHui Instruments). Adapted from Taylor et al. (2017)<ref>Taylor, S., Becher, J., Beal, S., Ringelberg, D., Spanggord, R., and Dontsova, K., 2017. Photo-transformation of explosives and their constituents. In: The Environmental Aspects of Munitions Workshop, Joint Army-Navy-NASA-Air Force (JANNAF), Kansas City, MO, May 22, 2017.</ref>.]]
 
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For a chemical bond to break via direct photolysis, a molecule must absorb a photon with higher energy than the energy of the bond. The energy of photons in the UV-Vis range is similar to the bond energies of several single [[wikipedia:Covalent_bond|covalent bonds]] found in organic molecules<ref name=":1" />. Therefore, many of the bonds in TNT, DNAN, NTO, and NQ are susceptible to photolysis from sunlight exposure (Figure 4).
 
  
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[[File: PhotolysisFig4.png | thumb | 650px | left | Figure 4. Calculated bond energies (black) and corresponding photon wavelengths (blue, determined from Planck’s equation<ref name=":1" />) required to break the bonds in TNT, DNAN, NTO, and NQ (calculations by Dr. Diego Troya<ref>Dontsova, K., Taylor, S., Brusseau, M. L., Simunek, J., and Hunt, E., 2017. Influence of climate on dissolution and phototransformation of NTO and DNAN from insensitive munitions and their fate in soils. In: Poster, the SERDP-ESTCP symposium, Washington, D.C., November 28-30, 2017. The Strategic Environmental Research and Development Program (SERDP) and Environmental Security Technology Certification Program (ESTCP).</ref>). Energies for bonds in the aromatic and heterocyclic rings are not shown because they exceed the maximum energy of the photons in sunlight reaching the Earth’s surface (500 kJ/mol or 239 nm).]]
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==References==
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<references />
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==Photolysis products and pathways==
 
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The products of the direct photolysis of MCs have been studied in depth, both in photoreactors using UV bulbs emitting light at a given wavelength (Figure 5) or wavelength ranges (including simulated sunlight) and outdoors in natural sunlight. The photolysis of MCs can form mineral products as well as transformation products that may be more toxic than the original compounds.
 
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[[File: PhotolysisFig5.png | thumb | 650px | left | Figure 5. Example of a UV photoreactor (A) with slots for UV bulbs (B) and a rotating carousel to hold samples (C). Reproduced with permission from [https://rayonet.org/ The Southern New England Ultraviolet Company].]]
 
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''TNT''
 
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The formation of pink and red wastewater released by some ammunition plants led to investigations into the photolysis products of TNT starting in the 1970s. Laboratory experiments observed rapid phototransformation from sunlight in natural waters, some with half-lives less than an hour<ref name=":3">Mabey, W.R., Tse, D., Baraze, A., and Mill, T., 1983. Photolysis of nitroaromatics in aquatic systems. I. 2,4,6-trinitrotoluene. Chemosphere, 12(1), pp. 3-16. [https://doi.org/10.1016/0045-6535(83)90174-1 doi: 10.1016/0045-6535(83)90174-1]</ref>. Numerous photolysis products of TNT have been reported and include, but are not limited to, 2-amino-4,6-dinitrobenzoic acid, 2,4,6-trinitrobenzaldehyde, 4,6-dinitroanthranil, 2,4,6-trinitrobenzonitrile, 2,4,6-trinitrobenzoic acid, [[wikipedia:1,3,5-Trinitrobenzene|1,3,5-trinitrobenzene]] (TNB), 2,4,6-trinitrobenzyl alcohol, and an array of [[wikipedia:Azo_compound|azo]] and [[wikipedia:Azoxy_compounds|azoxy]] compounds<ref name=":2" /><ref>Burlinson, N.E., Kaplan, L.A., and Adams, C.E., 1983.  Photochemistry of TNT: Investigation of the ‘pink water’ problem. Naval Ordnance Laboratory, pp. 73-172. [//www.enviro.wiki/images/c/ca/ADA1999.pdf Report]</ref><ref>Spanggord, R.J., Mill, T., Chou, T., Mabey, W.R., Smith, J.H., and Lee, S., 1980. Environmental fate studies on certain munition wastewater constituents. Phase II - Laboratory studies. U S Army Biomedical Research and Development Laboratory. [[Special:FilePath/ADA1980.pdf| Report]]</ref><ref name=":4">Spanggord, R.J., Mabey, W.R., Mill, T., Tsong-Wen, C., Smith, J.H., Lee, S., and Roberts, D., 1983. Environmental fate studies on certain munitions wastewater constituents: Phase IV - Lagoon model studies. U S Army Biomedical Research and Development Laboratory. [[Special:FilePath/ADA1983.pdf| Report]]</ref><ref name=":5">Luning Prak D.J., Breuer J.E.T., Rios E.A., Jedlicka E.E., and O'Sullivan D.W., 2017. Photolysis of 2,4,6-trinitrotoluene in seawater and estuary water: Impact of pH, temperature, salinity, and dissolved organic matter. Marine Pollution Bulletin, 114(2), pp. 977-986. [https://doi.org/10.1016/j.marpolbul.2016.10.073 doi: 10.1016/j.marpolbul.2016.10.073]</ref>.
 
  
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The mechanism of [[wikipedia:TNT|TNT]] photolysis is not completely understood as numerous products are formed, many of which are not readily synthesized or purchased<ref name=":5" />. However, evidence suggests that TNT is initially excited to a triplet state by [[wikipedia:Ultraviolet|UV]] light<ref name=":3" />. Figure 6 shows a proposed environmental reaction pathway for [[wikipedia:TNT|TNT]] that combines photo- and biological reactions based on studies in waste disposal lagoons<ref name=":4" />.
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==See Also==
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[[File: PhotolysisFig6.png | thumb | 650px | left | Figure 6. Proposed environmental transformation pathway for TNT, including phototransformation and biotransformation reactions. Image courtesy of the U.S. Army Engineer Research and Development Center<ref name=":4" /><ref>Walsh, M.E., 1990. Environmental Transformation Products of Nitroaromatics and Nitramines: Literature Review and Recommendations for Analytical Method Development. US Army Corps of Engineers Cold Regions Research and Engineering Laboratory. [[Special:FilePath/ADA1990.pdf| Report]]</ref>.]]
 
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The aquatic toxicity of phototransformed TNT solutions and ammunition wastewaters was not found to be significantly different from that of untransformed TNT<ref>Liu, D.H.W., Spanggord, R.J., Bailey, H.C., Javitz, H.S., and Jones, D.C.L., 1983. Toxicity of TNT Wastewaters to Aquatic Organisms. Volume 1. Acute Toxicity of LAP Wastewater and 2,4,6-Trinitrotoluene. U S Army Medical Bioengineering Research and Development Laboratory. [[Media: ADA1983-2.pdf | Report]]</ref><ref>Kennedy, A.J., Poda, A.R., Melby, N.L., Moores, L.C., Jordan, S.M., Gust, K.A., and Bednar, A.J., 2017. Aquatic toxicity of photo-degraded insensitive munition 101 (IMX-101) constituents. Environmental Toxicology and Chemistry, 36(8), pp.2050-2057. [https://doi.org/10.1002/etc.3732 doi: 10.1002/etc.3732]</ref>. Although TNT phototransformation products tend to be more toxic than TNT, the relatively low product formation coupled with the disappearance of TNT may explain these results.
 
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<references />
 

Latest revision as of 14:07, 25 April 2022

Climate change affects both terrestrial[1] and aquatic biomes[2] causing significant effects on ecosystem functions and biodiversity[3]. Climate change is affecting several key ecological processes and patterns that will have cascading impacts on wildlife and habitat[4]. For example, sea-level rise, changes in the timing and duration of growing seasons, and changes in primary production are mainly driven by changes to global environmental variables (e.g., temperature and atmospheric CO2). Climate-induced changes in the environment ultimately impact wildlife population abundance and distributions.

Related Article(s):


Contributor(s): Dr. Breanna F. Powers and Dr. Julie A. Heath


Key Resource(s):

  • Global climate change and wildlife in North America. Wildlife Society Technical Review 04-2[4]
  • Impacts of climate change on the future of biodiversity[3]

Introduction

Figure 1. The predicted extinction risk (by percentage with 95% CIs) from climate change by different regions, colors represent a gradient from least to most extinction risks (green to red) based upon the number of relevant studies (n). Figure is from Urban (2015)[5]. Reprinted with permission from AAAS. Any use of this figure requires the prior written permission of AAAS

Global climate change will affect ecosystem functions and cycles such as nutrient, hydraulic, and carbon cycles, changing aspects of environmental conditions such as temperature, soil moisture, and precipitation[6][7]. Wildlife species are adapted to their environments and changes to the environment and habitat conditions will mediate effects, either directly or indirectly, on species survival, fecundity and ultimately population persistence[8][9][10]. The ability to adapt to changing habitat conditions as a result of climate change will differ across individual species and between populations. Some wildlife species may be more vulnerable to climate change than other species (Figure 1). Vulnerability is often linked to particular life-history traits (e.g., specialized habitat needs or limited dispersal abilities, see Pacifici et al. 2015P[11] for a review on species vulnerability to climate change) or genetic composition. For example, grassland birds may be more vulnerable to changing climate than forest birds as forests can buffer change more so than grasslands[12]. Projected changes in the climate will generally have adverse effects of wildlife populations[13], though there are some species coping with climate change or benefitting from environmental change. For example, American kestrels (Falco sparverius) have shifted their breeding phenology to earlier in the year and may now raise two broods of young within a breeding season[14].

Figure 2. Conceptual diagram showing how increased water temperatures and pCO₂ (partial pressure of carbon dioxide) affect the early life stages of fish. Where arrow direction indicated increasing rate ( ↑ ), decreasing rate ( ↓ ), or both directions depending on other environmental variables ( ↕️ ). Figure is from Pankhurst and Munday (2011)[15].

The influence of climate change on wildlife and habitats

Climate change effects on wildlife include increases and changes in disease and pathogens distribution, patterns, and outbreaks in wildlife[16][17][18]; changes in range distributions and shifts in latitudinal and elevational gradients; changes in phenology or the timing of life cycle events that may create phenological mismatches[19]; and extinction or population reduction[5]. The effects of climate change across a species’ range will most likely not be homogenous, meaning it can vary substantially, especially if a species’ range spans across different continents as exhibited by many migratory birds. Other changes in habitat include shifting vegetation (i.e., tree-lines are shifting to higher elevations), changes in nutrients in plants, earlier snowmelt and run-off, increase in invasive species, warming of streams and rivers, reduction or degradation of habitat (i.e., glacial melt), and an increase in large wildfires[20]and droughts[21].

Although climate change effects on wildlife often are linked to species-specific traits, there are general impacts associated with taxonomic groups[4]. For fish it can affect reproduction[15], growth, and recruitment[22](Figure 2). Cold-water fish such as inland North American species are highly affected with the warming of streams and rivers[22]. Amphibians are highly sensitive to their environment and changes in temperature and moisture can affect development, range, abundance, and phenology[23][4][24]. In reptiles, climate change effects can alter thermoregulation patterns, affect female reproduction and in some species, change sex ratios with increasing temperature[4]. Furthermore, for many bird species the timing of migration and other phenological events are affected by climate change[25]. Range shifts, growth size, and survival are linked to climate change for mammals[4]. Arctic marine mammals are closely linked to sea ice dynamics and a changing climate will affect these dynamics[26]. Therefore, it is increasingly important for conservation and management plans to consider the effects of climate change on wildlife and habitat for the geographic location[27].

References

  1. ^ Diffenbaugh, N. S. and Field, C. B., 2013. Changes in Ecologically Critical Terrestrial Climate Conditions. Science, 341(6145), pp. 486-492. doi: 10.1126/science.1237123
  2. ^ Hoegh-Guldberg, O., and Bruno, J. F., 2010. The Impact of Climate Change on the World’s Marine Ecosystem. Science, 328(5985), pp. 1523-1528. doi: 10.1126/science.1189930
  3. ^ 3.0 3.1 Bellard, C., Berteslsmeier, C., Leadley, P., Thuiller, W., and Courchamp, F., 2012. Impacts of climate change on the future of biodiversity. Ecological Letters, 15(4), pp. 365-377. doi: 10.1111/j.1461-0248.2011.01736.x Article pdf
  4. ^ 4.0 4.1 4.2 4.3 4.4 4.5 Inkley, D. B., Anderson, M. G., Blaustein, A. R., Burkett, V. R., Felzer, B., Griffith, B., Price, J., and Root, T. L., 2004. Global Climate Change and Wildlife in North America. Wildlife Society Technical Review 04-2. The Wildlife Society, Bethesda, MD, 26 pp. Report pdf
  5. ^ 5.0 5.1 Urban, M. C., 2015. Accelerating extinction risk from climate change. Science, 348(6234), pp. 571-573. 10.1126/science.aaa4984 doi: 10.1126/science.aaa4984 Article pdf
  6. ^ Davidson, E. A. and Janssens, I. A., 2006. Temperature sensitivity of soil carbon decomposition and feedbacks to climate change. Nature, 440, pp. 165-173.doi: 10.1038/nature04514
  7. ^ Melillo, J. M., McGuire, A. D., Kicklighter, D. W., Moore, B., Vorosmarty, C. J., and Schloss, A. L., 1993. Global climate change and terrestrial net primary production. Nature, 363, pp. 234-240. doi: 10.1038/363234a0
  8. ^ Alig, R. J., Technical Coordinator, 2011. Effects of Climate Change on Natural Resources and Communities: A Compendium of Briefing Papers. U.S. Department of Agriculture, Forest Service, Pacific Northwest Research Station, General Technical Report, PNW-GTR-837, Portland, OR, 169p. doi:10.2737/PNW-GTR-837 Report pdf
  9. ^ Acevedo-Whitehouse, K., and Duffus, A. L. J., 2009. Effects of environmental change on wildlife health. Philosophical Transactions of the Royal Society B: Biological Sciences, 364(1534), pp. 3429-3438. doi: 10.1098/rstb.2009.0128
  10. ^ Milligan, S. R., Holt, W. V., and Lloyd, R., 2009. Impacts of climate change and environmental factors on reproduction and development in wildlife. Philosophical Transactions of the Royal Society B: Biological Sciences, 364(1534), pp. 3313-3319. doi: 10.1098/rstb.2009.0175 Article pdf
  11. ^ Pacifici, M., Foden, W., and Visconti, P., 2015. Assessing species vulnerability to climate change. Nature Climate Change 5, pp. 215-225. doi: 10.1038/nclimate2448
  12. ^ Jarzyna, M. A., Zuckerberg, B., Finley, A. O., and Porter, W. F., 2016. Synergistic effects of climate change and land cover: grassland birds are more vulnerable to climate change. Landscape Ecology, 31(10), pp. 2275-2290. doi: 10.1007/s10980-016-0399-1
  13. ^ IPCC, 2001. Climate Change 2001: Synthesis Report. A Contribution of Working Groups I, II, and III to the Third Assessment Report of the Intergovernmental Panel on Climate Change. R.T. Watson and the Core Writing Team (eds.). Cambridge University Press, Cambridge, United Kingdom, and New York, NY, USA, 398p. Report pdf
  14. ^ Smith, S. H., Steenhof, K., McClure, C. J. W., and Heath, J. A. 2017. Earlier nesting by generalist predatory bird is associated with human responses to climate change. Journal of Animal Ecology, 86(1), pp. 98-107. doi: 10.1111/1365-2656.12604 Article pdf
  15. ^ 15.0 15.1 Pankhurst, N. W., and Munday, P. L., 2011. Effects of climate change on fish reproduction and early life history stages. Marine and Freshwater Research, 62(9), pp. 1015-1026. doi: 10.1071/MF10269 Article pdf
  16. ^ Bradley, B. A., Wilcove, D. S., and Oppenheimer, M., 2010. Climate change increases risk of plant invasion in the Eastern United States. Biological Invasions, 12, pp.1855-1872. doi: 10.1007/s10530-009-9597-y
  17. ^ Cudmore, T. J., Björklund, N., Carroll, A. L., and Lindgren, B. S., 2010. Climate change and the range expansion of an aggressive bark beetle: evidence of higher beetle reproduction in naïve host tree populations. Journal of Applied Ecology, 47(5), pp. 1036-1043. doi: 10.1111/j.1365-2664.2010.01848.x Article pdf
  18. ^ Price, S. J., Leung, W. T., Owen, C. J., Puschendorf, R., Sergeant, C., Cunningham, A. A., Balloux, F., Garner, T. W., and Nichols, R. A., 2019. Effects of historic and projected climate change on the range and impacts of an emerging wildlife disease. Global Change Biology, 25(8), pp. 2648-2660. doi: 10.1111/gcb.14651
  19. ^ Renner, S. S., and Zohner, C. M., 2018. Climate Change and Phenological Mismatch in Trophic Interactions Among Plants, Insects, and Vertebrates. Annual Review of Ecology, Evolution, and Systematics, 49, pp. 165-182. doi: 10.1146/annurev-ecolsys-110617-062535
  20. ^ Barbero, R., Abatzoglou, J. T., Larkin, N. K., Kolden, C. A., and Stocks, B., 2015. Climate change presents increased potential for very large fires in the contiguous United States. International Journal of Wildland Fire, 24(7), pp. 892-899. doi: 10.1071/WF150830128 Article pdf
  21. ^ Schlaepfer, D. R., Bradford, J. B., Lauenroth, W. K., Munson, S. M., Tietjen, B., Hall, S. A., Wilson, S. D., Duniway, M. C., Jia, G., Pyke, D. A., Lkhagva, A., and Jamiyansharav, K., 2017. Climate change reduces extent of temperate drylands and intensifies drought in deep soils. Nature Communications, 8, pp. 14196. doi: 10.1038/ncomms14196
  22. ^ 22.0 22.1 Lynch, A. J., Myers, B. J. E., Chu, C., Eby, L. A., Falke, J. A., Kovach, R. P., Krabbenhoft, T. J., Kwak, T. J., Lyons, J., Paukert, C. P., and Whitney, J. E., 2016. Climate Change Effects on North American Inland Fish Populations and Assemblages. Fisheries, 41(7), pp. 346-361. doi: 10.1080/03632415.2016.1186016
  23. ^ Blaustein, A.R., Walls, S.C., Bancroft, B.A., Lawler, J.J., Searle, C.L., and Gervasi, S.S., 2010. Direct and Indirect Effects of Climate Change on Amphibian Populations. Diversity, 2(2), pp. 281-313.doi: 10.3390/d2020281 Article pdf
  24. ^ Ficetola, G. F., and Maiorano, L., 2016. Contrasting effects of temperature and precipitation change on amphibian phenology, abundance and performance. Oecologia, 181(3), pp. 683-693. doi: 10.1007/s00442-016-3610-9
  25. ^ Crick, H. Q. P., 2004. The impact of climate change on birds. Ibis, 146(s1), pp. 48-56. doi: 10.1111/j.1474-919X.2004.00327.x Article pdf
  26. ^ Kovacs, K. M., Lydersen, C., Overland, J. E., and Moore, S. E., 2011. Impacts of changing sea-ice conditions on Arctic marine mammals. Marine Biodiversity, 41, pp. 81-194. doi: 10.1007/s12526-010-0061-0
  27. ^ Mawdsley, J. R., O’Malley, R., and Ojima, D. S. 2009. A Review of Climate-Change Adaptations Strategies For Wildlife Management and Biodiversity Conservation. Conservation Biology, 23(5), pp. 1080-1089. doi: 10.1111/j.1523-1739.2009.01264.x

See Also

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