Chemosphere 191 (2018) 990e1007 Contents lists available at ScienceDirect Chemosphere journal homepage: www.elsevier.com/locate/chemosphere Review Pyrethroid pesticide residues in the global environment: An overview Wangxin Tang, Di Wang, Jiaqi Wang, Zhengwen Wu, Lingyu Li, Mingli Huang, Shaohui Xu, * Dongyun Yan College of Environmental Sciences and Engineering, Qingdao University, Qingdao, 266071, China highlights Pyrethroid pesticides have been widely detected at the global scale. Sediment samples from developed regions revealed high levels of pyrethroids. Pesticide residues in residential environments and the human body should be given more attention. article info abstract Article history: Pyrethroids are synthetic organic insecticides with low mammalian toxicity that are widely used in both Received 12 July 2017 rural and urban areas worldwide. After entering the natural environment, pyrethroids circulate among Received in revised form the three phases of solid, liquid, and gas and enter organisms through food chains, resulting in sub- 17 October 2017 stantial health risks. This review summarized the available studies on pyrethroid residues since 1986 in Accepted 20 October 2017 different media at the global scale and indicated that pyrethroids have been widely detected in a range of Available online 23 October 2017 environments (including soils, water, sediments, and indoors) and in organisms. The concentrations and Handling Editor: Frederic Leusch detection rates of agricultural pyrethroids, which always contain a-cyanogroup (a-CN), such as cyper- methrin and fenvalerate, decline in the order of crops > sediments > soils > water. Urban pyrethroids Keywords: (not contain a-CN), such as permethrin, have been detected at high levels in the indoor environment, and Pyrethroids 3-phenoxybenzoic acid, a common pyrethroid metabolite in human urine, is frequently detected in the Residue distributions human body. Pyrethroid pesticides accumulate in sediments, which are a source of pyrethroid residues in Transport pathways aquatic products. Ecological risks © 2017 Elsevier Ltd. All rights reserved. Contents 1. Introduction . ....................... 991 2. Spatiotemporal variation in pyrethroids in species and their frequency of detection . ....................... 991 3. Pyrethroid residues in environmental media . ....................... 992 3.1. Pyrethroid residues in soils . ..........................................992 3.2. Pyrethroid residues in surface water . ..........................................993 3.3. Pyrethroid residues in sediments . .. ..........................................995 3.4. Indoor pyrethroid residues . ..........................................996 3.5. Pyrethroid residues in crops . ..........................................998 3.6. Pyrethroid residues in aquatic organisms . ......................................998 3.7. Pyrethroid residues in land organisms and their secretions . ...........................999 3.8. Pyrethroids and their metabolite residues in the human body . ...........................999 4. Pathways of pyrethroid transportation . ...................... 1001 5. Conclusions . ...................... 1002 Acknowledgments . .................................................1002 * Corresponding author. No. 308 Ningxia Road, College of Environmental Sciences and Engineering, Qingdao University, Qingdao, China. E-mail address: [email protected] (D. Yan). https://doi.org/10.1016/j.chemosphere.2017.10.115 0045-6535/© 2017 Elsevier Ltd. All rights reserved. W. Tang et al. / Chemosphere 191 (2018) 990e1007 991 Supplementary data . ............................................... 1002 References................................................................ ................................. ......................1002 1. Introduction provide a technical basis for future ecological risk assessments and pollution management. Pyrethroids are a class of synthetic organic insecticides derived from pyrethrins. They have been used worldwide since the 1980s 2. Spatiotemporal variation in pyrethroids in species and because of their high level of effectiveness and low toxicity their frequency of detection compared to other insecticides, such as organophosphorus and carbamic ester compounds (Yoo et al., 2016). Pyrethroid pesticides We reviewed the reported levels of pyrethroids and their me- had become one of the three major kinds of pesticides (Xiao et al., tabolites in various environmental media (soils, water, and sedi- 2012), and the global synthetic pyrethroids market is valued at ments) and organisms (plants, animals, and humans). In total, 31 $1633.03 million in 2016 (QYResearch Group, 2017). Based on their pyrethroids and 8 metabolites were reported in these media. molecular structure, they can be divided into agricultural pyre- Cypermethrin was the most frequently detected pyrethroid (102 throids (alpha-, with medium toxicity) and urban pyrethroids (not times: see Table $1), followed by permethrin (73 times), delta- containing alpha-, with low toxicity), which are primarily used for methrin (66 times), fenvalerate (59 times), and bifenthrin (57 agriculture and nonagricultural pest control, respectively. Pyre- times), all of which are commonly used. Cyphenothrin, kadethrin, throids also play a vital role in personal care products such as tefluthrin, and bioallethrin were reported only once in water shampoo and mosquito-repellent perfume. Cypermethrin, delta- samples. b-cyfluthrin was reported only once in sediments. Fur- methrin, fenpropathrin, fenvalerate, bifenthrin, permethrin, l- amethrin, transfluthrin, and metofluthrin were reported only once cyhalothrin, and cyfluthrin have been widely used in recent years in and around homes, while 3-PBA was the main pyrethroid (Gong, 2013). Compared to traditional pesticides, pyrethroid pes- metabolite reported in the human body. ticides have less potential to pollute the environment, but can enter Annual variation: Based on 176 published papers, we produced organisms through food chains. They are very toxic to aquatic or- graphs of the number of studies of pyrethroid residues and the ganisms and may cause long-term adverse effects in aquatic envi- highest concentrations reported in various media over the past ronments (Zhao, 2014). Due to the lipophilicity of pyrethroids, it is three decades (Fig. 1). Concentrations of water, indoor environment difficult to remove them once they enter an organism. Long-term, and human body were not included because of differences in the low-dose exposure to pyrethroids can cause chronic diseases and units. It should be noted that most of the studies included in this have toxic effects on the nervous, immune, cardiovascular, and review were published in the last 10 years (from 2007 to the pre- genetic systems of organisms, inducing teratogenicity, carcinoge- sent); therefore, the situation before 2007 may not have been nicity, and mutagenicity (Ma, 2009). Koureas et al. (2012) provided accurately represented. The number of studies of pyrethroid resi- evidence that pyrethroid exposure is associated with adverse ef- dues in the environment has increased over time. The two earliest fects on the male reproductive system. Radwan et al. (2015) found datasets were from indoor investigations in China (low concen- that urinary pyrethroid metabolite levels are significantly related to trations). Highest concentrations (trans-permethrin, sperm aneuploidy. In case-control studies in Shanghai and Shanxi À 375700.00 ng g 1) were detected in bed sediments in Osun, Nigeria, provinces in China, the geometric mean concentrations of urinary in 2016. pyrethroid metabolites of patients were higher than those of Fig. 2 shows the overall increasing trend in the detection of healthy children, indicating that exposure to pyrethroid pesticides pyrethroid residues over the past three decades. Between 2006 and may be associated with an increased risk of childhood brain tu- 2016, not including 2007 and 2010, more than or equal to 10 py- mors, childhood acute lymphocytic leukemia, and coronary heart rethroids were detected every year, and 2014 had the largest fre- disease (Ding et al., 2012; Chen et al., 2016; Han et al., 2017). In quencies of detection of 16 pyrethroids, as shown in Fig. 2. The addition, children with urinary 3-phenoxybenzoic acid (3-PBA) frequency of detection of agricultural pyrethroids was greater than levels above the limit of detection (LOD) are twice as likely to have that of urban pyrethroids, but the frequency of detection of both attention deficit hyperactivity disorder compared to those with groups increased during the past three decades. Annual variation urinary 3-PBA levels below the LOD. Moreover, hyperactive- over the past decade is not obvious, probably because the degra- impulsive symptoms increased by 50% for every 10-fold increase dation rate of pyrethroid pesticides changes with different envi- in 3-PBA levels (Wagner-Schuman et al., 2015). In 2015, pesticides ronmental conditions and environmental regulations. The were measured in carpet dust from the houses of 277 children with difference in pyrethroid residence time in different environments leukemia and 306 controls in northern and central California, might be another important reason for the lack of obvious annual United States, where pyrethroid residues were derived from home variation. and garden pest treatments. Cyfluthrin and cypermethrin were Regional differences: Pyrethroids have been widely detected at detected in 25.0% and 49.0% of the homes,