Clinton F. Williams

Uptake of Three Antibiotics and an Antiepileptic Drug by Wheat Crops Spray Irrigated with Wastewater Treatment Plant Effluent

With rising demands on water supplies necessitating water reuse, wastewater treatment plant (WWTP) effluent is often used to irrigate agricultural lands. Emerging contaminants, like pharmaceuticals and personal care products (PPCPs), are frequently found in effluent due to limited removal during WWTP processes. Concern has arisen about the environmental fate of PPCPs, especially regarding plant uptake. The aim of this study was to analyze uptake of sulfamethoxazole, trimethoprim, ofloxacin, and carbamazepine in wheat ( L.) plants that were spray-irrigated with WWTP effluent. Wheat was collected before and during harvest, and plants were divided into grain and straw. Subsamples were rinsed with methanol to remove compounds adhering to surfaces. All plant tissues underwent liquid-solid extraction, solid-phase extraction cleanup, and liquid chromatography-tandem mass spectrometry analysis. Residues of each compound were present on most plant surfaces. Ofloxacin was found throughout the plant, with higher concentrations in the straw (10.2 ± 7.05 ng g) and lower concentrations in the grain (2.28 ± 0.89 ng g). Trimethoprim was found only on grain or straw surfaces, whereas carbamazepine and sulfamethoxazole were concentrated within the grain (1.88 ± 2.11 and 0.64 ± 0.37 ng g, respectively). These findings demonstrate that PPCPs can be taken up into wheat plants and adhere to plant surfaces when WWTP effluent is spray-irrigated. The presence of PPCPs within and on the surfaces of plants used as food sources raises the question of potential health risks for humans and animals.

Soil persistence and fate of carbamazepine, lincomycin, caffeine, and ibuprofen from wastewater reuse.

The reuse of treated wastewater for groundwater recharge is an effective way to provide advanced treatment and water storage. Contaminants such as human drugs have been identified as a potential problem for use of this water. Gilbert, Arizona maintains a 28.3-ha facility designed to recharge 15,150 m d through recharge basins constructed on native soil. The facility averages an infiltration rate of >5 cm d, resulting in the potential of pharmaceutical compounds leaching to groundwater. One 4-ha basin was selected for spatial sampling of four pharmaceutically active compounds (PhACs). The compounds were carbamazepine, lincomycin, ibuprofen, and caffeine. Soils were extracted and analyzed using pressurized liquid extraction and liquid chromatography-mass spectrometry-mass spectrometry. The concentration of ibuprofen was below detection limits in all samples. Lincomycin exhibited no net accumulation from year to year but had significantly higher concentrations from depths of 0 to 5 cm than from depths >10 cm. Carbamazepine had the lowest concentration at 0 to 5 cm (0.18 ng g soil), providing evidence that there is potential degradation of carbamazepine in surface soils. Carbamazepine also exhibited significant accumulation from year to year. Caffeine exhibited net accumulation and had higher concentrations in surface samples. The accumulation of PhACs in the soil beneath recharge basins indicates that PhACs are being removed from the infiltrating water and that, regarding ibuprofen and lincomycin, the treatment is sustainable due to the lack of accumulation. Regarding carbamazepine and caffeine, further investigations are needed to determine possible management and environmental conditions that could prevent accumulation.

Seasonal variation in accurate identification of Escherichia coli within a constructed wetland receiving tertiary-treated municipal effluent

As the reuse of municipal wastewater escalates worldwide as a means to extend increasingly limited water supplies, accurate monitoring of water quality parameters, including Escherichia coli (E. coli), increases in importance. Chromogenic media are often used for detection of E. coli in environmental samples, but the presence of unique levels of organic and inorganic compounds alters reclaimed water chemistry, potentially hindering E. coli detection using enzyme-based chromogenic technology. Over seven months, we monitored E. coli levels using m-Coli Blue 24 broth in a constructed wetland filled with tertiary-treated municipal effluent. No E. coli were isolated in the wetland source waters, but E. coli, total coliforms, and heterotrophic bacteria increased dramatically within the wetland on all sampling dates, most probably due to fecal inputs from resident wildlife populations. Confirmatory testing of isolates presumptive for E. coli revealed a 41% rate of false-positive identification using m-Coli Blue 24 broth over seven months. Seasonal differences were evident, as false-positive rates averaged 35% in summer, but rose sharply to 75% in the late fall and winter. Corrected E. coli levels were significantly correlated with electrical conductivity, indicating that water chemistry may be controlling bacterial survival within the wetland. This is the first study to report that accuracy of chromogenic media for microbial enumeration in reclaimed water may show strong seasonal differences, and highlights the importance of validation of microbiological results from chromogenic media for accurate analysis of reclaimed water quality.

Serum estrogenicity and biological responses in African catfish raised in wastewater ponds in Ghana.

Reuse of wastewater for aquaculture improves the efficient use of water and promotes sustainability but the potential effects of endocrine disrupting compounds including estrogens in wastewater are an emerging challenge that needs to be addressed. We examined the biological effects of wastewater-borne estrogens on African catfish (Clarias gariepinus) raised in a wastewater stabilization pond (WSP) of a functioning municipal wastewater treatment plant, a wastewater polishing pond (WWP) of a dysfunctional treatment plant, and a reference pond (RP) unimpacted by wastewater, located in Ghana. Measurements of estrogen concentrations in pond water by liquid chromatography/tandem mass spectrometry showed that mean 17 β-estradiol concentrations were higher in the wastewater ponds (WWP, 6.6 ng/L±2.7 ng/L; WSP, 4.9 ng/L±1.0) than the reference (RP, 3.4±1.1 ng/L). Estrone concentrations were found to be highest in the WSP (7.8 ng/L±1.7) and lowest in the WWP (2.2 ng/L±2.4) with the RP intermediate (4.7±5.0). Fish serum estrogenicity assayed by E-SCREEN was significantly higher in female vs. male catfish in the RP and WSP but not in the WWP (p≤0.05). Histological examination of liver and gonad tissue showed no apparent signs of intersex or pathology in any ponds. The similarities in various measures of body indices between fish of this study and African catfish from freshwater systems suggest that aquaculture may be a suitable reuse option for treated municipal wastewater.

Septic systems as hot-spots of pollutants in the environment: Fate and mass balance of micropollutants in septic drainfields

Septic systems, a common type of onsite wastewater treatment systems, can be an important source of micropollutants in the environment. We investigated the fate and mass balance of 17 micropollutants, including wastewater markers, hormones, pharmaceuticals and personal care products (PPCPs) in the drainfield of a septic system. Drainfields were replicated in lysimeters (1.5m length, 0.9m width, 0.9m height) and managed similar to the field practice. In each lysimeter, a drip line dispersed 9L of septic tank effluent (STE) per day (equivalent to 32.29L/m(2) per day). Fourteen micropollutants in the STE and 12 in the leachate from drainfields were detected over eight months. Concentrations of most micropollutants in the leachate were low (<200ng/L) when compared to STE because >85% of the added micropollutants except for sucralose were attenuated in the drainfield. We discovered that sorption was the key mechanism for retention of carbamazepine and partially for sulfamethoxazole, whereas microbial degradation likely attenuated acetaminophen in the drainfield. This data suggests that sorption and microbial degradation limited transport of micropollutants from the drainfields. However, the leaching of small amounts of micropollutants indicate that septic systems are hot-spots of micropollutants in the environment and a better understanding of micropollutants in septic systems is needed to protect groundwater quality.

Comparison of equilibrium and non-equilibrium distribution coefficients for the human drug carbamazepine in soil

The distribution coefficient (KD) for the human drug carbamazepine was measured using a non-equilibrium technique. Repacked soil columns were prepared using an Airport silt loam (Typic Natrustalf) with an average organic matter content of 2.45%. Carbamazepine solutions were then leached through the columns at 0.5, 1.0 and 1.5 mL min(-1) representing average linear velocities of 1.8, 3.5 and 5.3 cm h(-1) respectively. Each flow rate was replicated three times and three carbamazepine pulses were applied to each column resulting in a total of 9 columns with 27 total carbamazepine pulses. Breakthrough curves were used to determine KD using the parameter fitting software CXTFIT. Results indicate that as flow rate decreased from 5.3 to 1.8 cm h(-1), KD increased an average of 21%. Additionally, KD determined by column leaching (14.7-22.7 L kg(-1)) was greater than KD determined by a 2h batch equilibrium adsorption (12.6 L kg(-1)). Based on these KDs carbamazepine would be generally characterized as non-mobile in the soil investigated. However, repeated carbamazepine applications resulted in an average 22% decrease in KD between the first and third applications. Decreasing KD is attributed to differences in sorption site kinetics and carbamazepine residence time in contact with the soil. This would indicate that the repeated use of reclaimed wastewater at high application rates for long-term irrigation or groundwater recharge has the potential to lead to greater transport of carbamazepine than KD determined by batch equilibrium would predict.

Sorption/Desorption of lincomycin from three arid-region soils.

The antibiotic lincomycin is commonly found in treated municipal waste water and in waste from swine and poultry production. Environmental disposal of these wastes has the potential to introduce a significant mass of lincomycin into the ecosystem. In the present study, a series of sorption and desorption experiments were conducted to determine the potential mobility of lincomycin in soils from arid environments. Sorption and desorption isotherms were obtained for lincomycin using three different soils. Isotherms were fit to the Freundlich equation. Adsorption of lincomycin was found to have a of 11.98 for a biosolid-treated soil (1.58% OC) and a of 210.15 for a similar unamended soil (1.42% OC). It was also found that for a low-organic-content soil the was 5.09. The differences in adsorption can be related to the soil pH and the pKa of lincomycin (7.5-7.8). When the soil solution pH is below the pKa, the cationic species of lincomycin dominates, resulting in increased water solubility. Interaction with the cation exchange complex is minimal due to a high solution cation concentration (Ca and Na). Desorption isotherms also indicate that when the solution pH is lower than the pKa, retention of lincomycin is reduced. Our results indicate that the mobility of lincomycin in these arid region soils is dependent on soil pH.

Development of Antibiotic Resistance in Bacteria of Soils Irrigated with Reclaimed Wastewater

Wastewater reclamation for municipal irrigation is an increasingly attractive option for extending water supplies. However, public health concerns include the potential for development of antibiotic resistance (AR) in soil bacteria after exposure to residual chemicals in reclaimed water. Though scientific studies have reported high levels of AR in soils irrigated with wastewater, these works often ignore the natural occurrence of soil AR. We are comparing AR patterns in soil Enterococcus isolated from water storage basins recharged with either reclaimed water or groundwater in central Arizona. Resistance to 16 antibiotics is being quantified from the soil surface (0-5 cm) to a depth of 30 cm. Results reveal that resistance to multiple antibiotics, including tetracycline, daptomycin, and erythromycin, exists in soils regardless of the water source (groundwater, reclaimed water). Though resistance patterns differ between bacteria isolated from soils from the two treatments, overall AR is not increased in soils exposed to reclaimed water. Comparing the development of AR in soil bacteria at these two sites will increase awareness of the environmental and public health impacts of using reclaimed water for irrigation of municipal areas.

Nitrogen Management Affects Nitrous Oxide Emissions under Varying Cotton Irrigation Systems in the Desert Southwest, USA

Irrigation of food and fiber crops worldwide continues to increase. Nitrogen (N) from fertilizers is a major source of the potent greenhouse gas nitrous oxide (NO) in irrigated cropping systems. Nitrous oxide emissions data are scarce for crops in the arid western United States. The objective of these studies was to assess the effect of N fertilizer management on NO emissions from furrow-irrigated, overhead sprinkler-irrigated, and subsurface drip-irrigated cotton ( L.) in Maricopa, AZ, on Trix and Casa Grande sandy clay loam soils. Soil test- and canopy-reflectance-based N fertilizer management were compared. In the furrow- and overhead sprinkler-irrigated fields, we also tested the enhanced efficiency N fertilizer additive Agrotain Plus as a NO mitigation tool. Nitrogen fertilizer rates as liquid urea ammonium nitrate ranged from 0 to 233 kg N ha. Two applications of N fertilizer were made with furrow irrigation, three applications under overhead sprinkler irrigation, and 24 fertigations with subsurface drip irrigation. Emissions were measured weekly from May through August with 1-L vented chambers. NO emissions were not agronomically significant, but increased as much as 16-fold following N fertilizer addition compared to zero-N controls. Emission factors ranged from 0.10 to 0.54% of added N fertilizer emitted as NO-N with furrow irrigation, 0.15 to 1.1% with overhead sprinkler irrigation, and <0.1% with subsurface drip irrigation. The reduction of NO emissions due to addition of Agrotain Plus to urea ammonium nitrate was inconsistent. This study provides unique data on NO emissions in arid-land irrigated cotton and illustrates the advantage of subsurface drip irrigation as a low NO source system.

Assessment of Soil to Mitigate Antibiotics in the Environment Due to Release of Wastewater Treatment Plant Effluent

With low levels of human antibiotics in the environment due to release of wastewater treatment plant (WWTP) effluent, concern is rising about impacts on human health and antibiotic resistance development. Furthermore, WWTP effluent may be released into waterways used as drinking water sources. The aim of this study was to analyze three antibiotics important to human health (sulfamethoxazole, ofloxacin, and trimethoprim) in soil and groundwater at a long-term wastewater reuse system that spray irrigates effluent. Soil samples were collected (i) at a site that had not received irrigation for 7 mo (approximate background concentrations), and then at the same site after (ii) one irrigation event and (iii) 10 wk of irrigation. Water samples were collected three times per year to capture seasonal variability. Sulfamethoxazole was typically at the highest concentrations in effluent (22 ± 3.7 μg L) with ofloxacin and trimethoprim at 2.2 ± 0.6 and 1.0 ± 0.02 μg L, respectively. In the soil, ofloxacin had the highest background concentrations (650 ± 204 ng kg), whereas concentrations of sulfamethoxazole were highest after continuous effluent irrigation (730 ± 360 ng kg). Trimethoprim was only quantified in soil after 10 wk of effluent irrigation (190 ± 71 ng kg). Groundwater concentrations were typically <25 ng L with high concentrations of 660 ± 20 and 67 ± 7.0 ng L for sulfamethoxazole and ofloxacin, respectively. Given that antibiotics interacted with the soil profile and groundwater concentrations were frequently about 1000-fold lower than effluent, soil may be an adequate tertiary treatment for WWTP effluent leading to improved water quality and protection of human health.