Copper Products (general information)
Copper is one of the most toxic heavy metals to fish (Nowak and Duda 1996), and is broadly toxic to the salmon olfactory system (Baldwin et al. 2003), potentially inhibiting the ability of juveniles to avoid predators or to find food (DeForest et al. 2010). Hara et al. (1976) documented that copper is a neurobehavioral toxicant in fish that disrupts the normal function of the fish olfactory system. Dissolved copper damages the olfactory sensory epithelium (Moran et al. 1992; Julliard et al. 1996; Hansen et al. 1999a; Beyers and Farmer 2001). Copper interferes with the ability of fish to detect and respond to chemical signals in aquatic environments (Hara et al. 1976; Saucier et al. 1994; Hansen et al. 1999b; Beyers and Farmer 2001; Baldwin et al. 2003; Sandahl et al. 2004; Carreau and Pyle 2005).
Copper impairs gill gas exchange, upsets salt balance, negatively affects reproductive output and the immune system, affects glucose metabolism and the cellular structure of fish, and negatively affects liver and kidney function (Ferguson and Sandoval 2020). The proposed low and high application rates are well above the range of salmonids and their prey LC50 (96 hour), and the LC50 (96 hour) for pond snails falls at the lowest proposed application rate (TOXNET 1975–1986). For salmonids, the upper recommended limit is < 0.03 mg/l in hard water (>100 mg/l CaCO3) whereas in soft water, it is <0.0006 mg/l (Ferguson and Sandoval 2020).
Freshwater fish acutely exposed to copper can experience disturbances of ion regulation and ammonia excretion (Macpherson and Cremazy 2024). Acute copper exposure decreased fish survival in Brook Char, inhibited Na+ influx, transiently promoted Cl- loss, and transient inhibition of ammonia clearance (Macpherson and Cremazy 2024).
Baldwin et al. (2011) documented that naturally reared steelhead (O. mykiss) exposed to nominal copper concentrations of 5 and 20 µg/L for 3 hours exhibited a concentration-dependent loss in olfactory function.
The sensory physiology and predator avoidance behaviors of juvenile coho were both significantly impaired by copper at concentrations as low as 2 µg/L (Sandahl et al. 2007).
Juvenile coho exposed to low levels of dissolved copper (5-20 µg/L) and then presented with cues signaling proximity of a predator exhibited no alarm response when exposed to copper, and cutthroat trout were more effective predators on copper-exposed coho during predation trials, as measured by attack latency, survival time, and capture success rate. Copper-exposed coho are unresponsive to their chemosensory environment, unprepared to evade nearby predators, and significantly less likely to survive an attack sequence (McIntyre et al. 2012).
In a study to assess susceptibility of Chinook Salmon and Rainbow Trout to infection with Vibrio anguillarum following sublethal copper exposure (Baker and Knittel 1983), higher concentrations of copper produced peak susceptibility to infection in shorter time periods. Rainbow Trout stressed by copper required 50% fewer pathogens to induce a fatal infection than non-copper exposed fish (Baker and Knittel 1983).
Fish eggs are more resistant than young fish fry to the toxic effects of copper sulfate (Gangstad 1986).
Juvenile Rainbow Trout were exposed to either hard water, or soft water, spiked with copper for 30 days (Taylor et al. 2000). Fish in the hard-water, high dose (60 µg/L) treatment groups showed an increased sensitivity to copper.
The mean 96-hour LC50 (with 95% confidence limits) for copper exposure in alevin, swim-up, parr and smolt Steelhead (Salmo gairdneri) are 28 (27–30), 17 (15–19), 18 (15–22), and 29 (>20) µg/L of copper respectively (Chen and Lin 2001). The mean 96-hour LC50 for copper exposure in alevin, swim-up, parr and smolt Chinook salmon are 26 (24–33), 19 (18–21), 38 (35–44), and 26 (23–35) µg/L of copper respectively. The experiments were done by adding copper as CuCl2.
The 48-hour LC50 for Fathead Minnow is 19.2 + 3.1 (mean + SD) mcg/L Cu (Mastin and Rodgers 2000).
EarthTec QZ
According to the label for EarthTec QZ, “this pesticide is toxic to fish and aquatic invertebrates. Waters treated with this product may be hazardous to aquatic organisms. Treatment of aquatic weeds and algae can result in oxygen loss from decomposition of dead algae and weeds. This oxygen loss can cause fish and invertebrate suffocation. Do not use this product in waters with cyprinid and salmonid fish.” EarthTec is produced in the cupric ion form, the most toxic form of copper (Ferguson and Sandoval 2020).Direct bioassay of Rainbow Trout (assumed adult) subject to EarthTec QZTM resulted in a NOEC of 0.240 mg/L copper, and LC50 of 0.294 mg/L copper. The EPA maximum allowable dose is 1 mg/L. Fish kills have been reported after copper sulfate applications for algae control in ponds and lakes, however, oxygen depletion and dead organisms clogging the gills have been cited as the cause of fish deaths, resulting from massive and sudden plant death and decomposition in the water body (Bartsch 1954, Hanson and Stefan 1984, Masser et al. 2006). Copper can either temporarily, or permanently, disrupt olfaction in fish (Solomon 2009, Ferguson and Sandoval 2020), possibly interfering with their ability to locate food, predators, and spawning streams (Chapman 1978, Jaensson and Olsen 2010). It is unknown if there are any bioaccumulation effects of EarthTec QZTM; one recent study suggested the fate of copper in the environment is not fully known and should be considered (Lake-Thompson and Hofmann 2019).
Copper Ethanolamine Complex (e.g., Natrix, Cutrine Plus)
Natrix
The active ingredient in SePRO's Natrix, registered for the control of mollusks in still or flowing waters as well as crop and non-crop irrigation and drainage systems and chemigation systems, is Copper Ethanolamine Complex (28.2%), EPA Reg. # 67690-81. Per its label, "Unlike most organic pesticides, copper is an element and will not break down in the environment and will therefore accumulate with repeated applications. Copper is a micronutrient, but its pesticidal application rate exceeds the amount of copper needed as a nutrient."
Label environmental hazards: "This pesticide is toxic to fish and aquatic invertebrates. Waters treated with this product may be hazardous to aquatic organisms. Treatment in areas with dense aquatic weeds and algae can result in oxygen loss from decomposition of dead algae and weeds. This oxygen loss can cause fish and invertebrate suffocation. To minimize this hazard, do not treat more than ½ of the water body to avoid depletion of oxygen due to decaying vegetation. Do not make applications less than 14 days apart." "Certain water conditions including low pH (<6.5), low dissolved organic carbon (DOC) levels (3.0 mg/L or lower), and “soft” waters (i.e. alkalinity less than 50 mg/L), increases the potential acute toxicity to non-target aquatic organisms. Fish toxicity generally decreases when the hardness of water increases. Do not use in waters containing trout or other fish species that are highly sensitive to copper if the alkalinity is less than 50 ppm, pH values are <6.5, and DOC levels >3.0."
According to the Safety Data Sheet for Natrix, toxicological effects on rabbits (dose >2000 mg/kg) = LD50 dermal and rats (dose 590 mg/kg) = LD50 oral. Natrix has been demonstrated to be a several irritant to the eyes of rabbits @ 0.1 ml exposure and a severe irritant to the skin of rabbits @ 0.5 ml.
Natrix is comprised of 14.9% copper triethanolamine complex, 13.3% copper monoethanolamine complex, and 4 proprietary ingredients (3 of them range from 10-30% and one ranges from 30-60%).
Proprietary ingredient 1:
Crustaceans - Ceriodaphnia dubia Neonate - exposed for 48 hours (acute EC50 609.98 mg/L fresh water), fish - Pimephales promelas - exposed for 96 hours (acute LC50 11800 mg/L fresh water), and daphnia - Daphnia magna - exposed for 21 days (chronic NOEC 16 mg/L fresh water).
Proprietary ingredient 2:
Algae - Isochrysis galbana - exposed for 96 hours (acute EC50 80 mg/L fresh water), adult crustaceans - Crangon crangon - exposed for 48 hours (acute LC50>100 mg/L marine water), fish - Carassius auratus - exposed for 96 hours (acute LC50 170 mg/L fresh water)
Proprietary ingredient 3:
Crustaceans - Ceriodaphnia dubia - Neonate - exposed for 48 hours (acute EC50 4.53 mg/L fresh water)
Cutrine Plus
The active ingredient in Cutrine Plus is copper ethanolamine complex. According to the product label, "This copper product is toxic to fish and aquatic organisms. Unlike most organic pesticides, copper is an element and will not break down in the environment and will therefore accumulate in sediment with repeated applications. Copper is a micronutrient, but its pesticidal application rate exceeds the amount of copper needed as a nutrient. Do not use in waters containing Koi and hybrid goldfish. Not intended for use in small volume, garden pond systems. Avoid treating waters with pH values <6.5, DOC levels >3.0, and alkalinity less than 50 ppm (e.g., soft or acid waters), as trout and other sensitive species of fish may be killed under such conditions if present."
According to the Safety Data Sheet for Cutrine Plus, acute oral toxicity in rats (LC50) is believed to be 1,000 mg/kg (acute toxicity estimate is >40 mg/l @ an exposure time of 4 hours. Acute dermal toxicity in rabbits (LD50) is >5,000 mg/kg.
Duke (2007) documented both laboratory and field responses of target and non-target species to algaecide exposures, including exposure to Cutrine Plus. Ceriodaphnia dubia exposed to Cutrine Plus @ a concentration of 54 µg acid-extractable Cu/L resulted in 96-h LC50 and @ a concentration of 70 µg acid-extractable Cu/L resulted in 96-h EC50. Murray-Gulde (2002) documented a concentration of 124 µg acid-extractable Cu/L resulted in 96-h LC50.
Pimephales promelas exposed to Cutrine Plus concentrations of 731 and 973 µg acid-extractable Cu/L resulted in 96-h LC50 (Duke 2007). Murray-Gulde (2002) documented Cutrine Plus concentrations of 863 µg acid-extractable Cu/L resulted in 96-h EC50. Mastin and Rodgers (2000) documented a Cutrine Plus concentration of 255.4 µg acid-extractable Cu/L resulted in 48-h EC50.
Mastin and Rodgers (2000) documented the toxicity and bioavailability of copper herbicides, including Cutrine-Plus and copper sulfate, to freshwater animals 7 days after initial herbicide applications. Aqueous 48-h toxicity experiments were performed to contrast responses of Daphnia magna Strauss, Hyalella azteca Saussure, Chironomus tentans Fabricius, and Pimephales promelas Rafinesque to Cutrine(R)-Plus. 48-h LC50s for organisms exposed to Cutrine-Plus was 11.3 µg Cu/L. Organisms exposed to Cutrine-Plus and copper sulfate had exposure-response slopes of 8.61 and 5.07% mortality/µg Cu/L, respectively. Bioavailability of Cutrine-Plus was determined by comparing survival data (LC50s) of test organisms exposed to herbicide concentrations during the first and last 48-h of a 7-day exposure period. Even in these relatively simplified water-only exposures, a transformation of copper to less bioavailable species over time was observed with a 100-200% decrease in toxicity (i.e., an increase in 48-h LC50s) for all four test animals. This series of laboratory experiments provides a worst-case scenario for determining the risk associated with the manufacturer's recommended application rates of Cutrine-Plus (200-1,000 microg Cu/L) and copper sulfate (100-500 microg Cu/L) in natural waters for four nontarget freshwater animals.
The EPA Ecotox database includes 7 research studies associated with copper ethanolamine complex:
Water flea (Daphnia magna) less than 24 hours old were exposed to 0.82 (0.56-0.94) AI mg/L and 0.2 AI mg/L in the lab in flow-through fresh water conditions, and EC50 was 2 days and no observed effective level (NOEL) was observed after 2 days, respectively (US EPA 1992).
Rainbow trout (Oncorhynchus mykiss) were exposed to 1.5 (1.3-1.7) AI mg/L in the lab in flow-through freshwater conditions, and LC50 was observed after 4 days (US EPA 1992).
Bluegill (Lepomis macrochirus) were exposed to 2 AI mg/L and 4.2 (3.5-6) in the lab in flow-through fresh water conditions, and NOEL was observed after 4 days and mortality was observed after 4 days, respectively (US EPA 1992).