Occurrence of steroid sex hormones in the Cache la Poudre River: and pathways for the removal in the environment

Abstract

Some chemicals have the apparent ability to disrupt normal endocrine system functions after exposure to concentrations so small that they are difficult to detect in the environment. In recent years, these so-called "endocrine disruptors" have become the subject of intensive scientific research. In wildlife, most of the evidence for endocrine disruption has come from studies on species living in, or closely associated with, aquatic environments. Reported effects of endocrine disruption include abnormal blood hormone levels, masculinization of females, feminization of males, altered sex ratios, intersexuality, and reduced fertility and fecundity. Among suspected endocrine disruptors, exogenous steroid sex hormones generally have the highest potencies for disrupting normal steroid sex hormone functions. In a national reconnaissance study conducted by the U.S. Geological Survey (USGS) from 1999 to 2000, steroid sex hormones were detected at varying concentrations and frequencies in water samples from 139 stream sites located in 30 states. Other studies have detected steroid sex hormones in surface waters throughout the world, including Colorado. Potential sources of steroid sex hormones in the environment include sewage treatment plants, septic systems, animal feeding operations, rangeland grazing, paper mills, aquaculture, and agricultural operations where manure and biosolids are applied as fertilizers. The objectives of this study were to investigate the presence of steroid sex hormones in northern Colorado's Cache la Poudre River, to determine the potential for steroid sex hormone biodegradation and photodegradation under natural conditions, and to characterize the mobility of selected steroid sex hormones in agricultural fields using a rainfall simulator. The study determined that steroid sex hormones are present in the Cache la Poudre River, at concentrations ranging from 0.6 ng L−1 (epitestosterone) to 22.6 ng L−1 (estrone). The study also determined that testosterone, progesterone, and 17β-estradiol can be degraded by manure-borne bacteria, and that testosterone degradation is faster under aerobic conditions and at higher temperatures (i.e., 37°C vs. 22°C), but little affected by changes in pH (from 6 to 7.5) or glucose amendments. In ultraviolet light λ > 340 nm, the study observed direct photodegradation of testosterone and progesterone, and indirect photodegradation of testosterone and 17β-estradiol in the presence of Elliot soil humic acid. On the other hand, in ultraviolet light λ > 310 nm, direct photodegradation of androstenedione was substantially faster than direct photodegradation of testosterone in ultraviolet light λ > 310 nm, and no indirect photodegradation observed. The study detected and identified three testosterone biodegradation products (dehydrotestosterone, androstenedione, and androstadienedione), and detected several products of testosterone and androstenedione photodegradation which appear to retain their steroid structure, and possibly their endocrine disrupting potential. Finally, the study generally observed that androgen runoff concentrations follow runoff rates and decrease after successive rainfall events, while runoff concentrations of other analytes (e.g., estrone) peak after the maximum runoff rate and first rainfall event. Sample and data analysis from the study are continuing, and comprehensive finding and recommendations are expected after the date of this report.