Wheelock Craig E, Miller Jeff L, Miller Mike J, Phillips Bryn M, Huntley Sarah A, Gee Shirley J, Tjeerdema Ronald S, Hammock Bruce D
Department of Entomology, Cancer Research Center, University of California at Davis, Davis, California 95616, USA.
Environ Toxicol Chem. 2006 Apr;25(4):973-84. doi: 10.1897/05-334r.1.
Increases in the use and application of pyrethroid insecticides have resulted in concern regarding potential effects on aquatic ecosystems. Methods for the detection of pyrethroids in receiving waters are required to monitor environmental levels of these insecticides. One method employed for the identification of causes of toxicity in aquatic samples is the toxicity identification evaluation (TIE); however, current TIE protocols do not include specific methods for pyrethroid detection. Recent work identified carboxylesterase treatment as a useful method for removing/detecting pyrethroid-associated toxicity. The present study has extended this earlier work and examined the ability of carboxylesterase activity to remove permethrin- and bifenthrin-associated toxicity to Ceriodaphnia dubia and Hyalella azteca in a variety of matrices, including laboratory water, Sacramento River (CA, USA) water, and Salinas River (CA, USA) interstitial water. Esterase activity successfully removed 1,000 ng/L of permethrin-associated toxicity and 600 ng/L of bifenthrin-associated toxicity to C. dubia in Sacramento River water. In interstitial water, 200 ng/L of permethrin-associated toxicity and 60 ng/L of bifenthrin-associated toxicity to H. azteca were removed. The selectivity of the method was validated using heat-inactivated enzyme and bovine serum albumin, demonstrating that catalytically active esterase is required. Further studies showed that the enzyme is not significantly inhibited by metals. Matrix effects on esterase activity were examined with municipal effluent and seawater in addition to the matrices discussed above. Results confirmed that the esterase retains catalytic function in a diverse array of matrices, suggesting that this technique can be adapted to a variety of aquatic samples. These data demonstrate the utility of carboxylesterase treatment as a viable step to detect the presence of pyrethroids in receiving waters.
拟除虫菊酯类杀虫剂使用和应用的增加引发了人们对其对水生生态系统潜在影响的担忧。需要有检测受纳水体中拟除虫菊酯的方法来监测这些杀虫剂的环境水平。毒性鉴定评估(TIE)是用于识别水生样品中毒性原因的一种方法;然而,目前的TIE方案并不包括检测拟除虫菊酯的具体方法。最近的研究确定羧酸酯酶处理是去除/检测与拟除虫菊酯相关毒性的一种有用方法。本研究扩展了早期的这项工作,并研究了羧酸酯酶活性在包括实验室用水、萨克拉门托河(美国加利福尼亚州)水和萨利纳斯河(美国加利福尼亚州)间隙水等多种基质中去除氯菊酯和联苯菊酯对蚤状溞和阿氏摇蚊相关毒性的能力。酯酶活性成功去除了萨克拉门托河水中1000 ng/L的氯菊酯相关毒性和600 ng/L的联苯菊酯对蚤状溞的相关毒性。在间隙水中,去除了200 ng/L的氯菊酯对阿氏摇蚊的相关毒性和60 ng/L的联苯菊酯相关毒性。使用热灭活酶和牛血清白蛋白验证了该方法的选择性,表明需要有催化活性的酯酶。进一步的研究表明,该酶不会受到金属的显著抑制。除了上述基质外,还使用城市污水和海水研究了基质对酯酶活性的影响。结果证实酯酶在多种不同的基质中都保留催化功能,这表明该技术可适用于各种水生样品。这些数据证明了羧酸酯酶处理作为检测受纳水体中拟除虫菊酯存在的可行步骤的实用性。