RESUMO

Long-term irrigation with untreated wastewater may increase soil microbial adaptation to pollution load and lead to enhanced natural attenuation. We hypothesized that long-term wastewater irrigation accelerates the dissipation of pharmaceuticals. To test our hypothesis we performed an incubation experiment with soils from the Mezquital Valley, Mexico that were irrigated for 0, 14, or 100 years. The results showed that the dissipation half-lives (DT50) of diclofenac (<0.1-1.4 days), bezafibrate (<0.1-4.8 days), sulfamethoxazole (2-33 days), naproxen (6-19 days), carbamazepine (355-1,624 days), and ciprofloxacin were not affected by wastewater irrigation. Trimethoprim dissipation was even slower in soils irrigated for 100 years (DT50: 45-72 days) than in nonirrigated soils (DT50: 12-16 days), was negatively correlated with soil organic matter content and soil-water distribution coefficients, and was inhibited in sterilized soils. Applying a kinetic fate model indicated that long-term irrigation enhanced sequestration of cationic or uncharged trimethoprim and uncharged carbamazepine, but did not affect sequestration of fast-dissipating zwitterions or negatively charged pharmaceuticals. We conclude that microbial adaptation processes play a minor role for pharmaceutical dissipation in wastewater-irrigated soils, while organic matter accumulation in these soils can retard trimethoprim and carbamazepine dissipation.

Assuntos

RESUMO

Wastewater irrigation is often performed by flood irrigation, leading to changes in redox potential (Eh) of irrigated soils. In addition to soil organic matter, Fe-(hydr)oxides are important sorbents for pollutants, and biotransformation of pollutants can be accelerated under reducing conditions. Here, the influence of reducing conditions on the release of sorbed pharmaceuticals from soil and their potential accelerated dissipation was investigated in a microcosm study. Samples of a soil from the Mezquital Valley (Mexico) irrigated for 85 yr with untreated wastewater were incubated under oxidizing (Eh of 500 ± 20 mV), weakly reducing (Eh of 100 ± 20 mV), and moderately reducing (Eh of -100 ± 20 mV) soil conditions for 30 to 31 d. The concentrations of nine pharmaceuticals (bezafibrate, carbamazepine, ciprofloxacin, sulfamethoxazole, trimethoprim, enrofloxacin, clarithromycin, diclofenac, and naproxen) were extracted via solid-phase extraction from soil slurries and analyzed by liquid chromatography-tandem mass spectrometry. Low Eh did not lead to a release of formerly sorbed pharmaceuticals from the wastewater irrigated soil. High pH values (>8) of the examined soil resulting from denitrification under reducing conditions prevented the dissolution of Fe-(hydr)oxides and, hence, the potential release of pharmaceuticals. A trend of decreasing concentrations of sulfamethoxazole and bezafibrate with time under moderately reducing conditions supports previous findings of a transformation of these compounds under anaerobic conditions.

RESUMO

As a consequence of population growth and urbanization, arable fields are increasingly irrigated with wastewater, but the related environmental and health risks (e.g., pollution with antibiotics) are poorly understood. We performed batch sorption experiments with sulfamethoxazole (SMX) and ciprofloxacin (CIP) and soils that had been irrigated with untreated wastewater for 0, 14, 35, and 100 yr. Sorption of CIP was always strong and largely irreversible irrespective of the duration of wastewater irrigation and the content and quality of soil organic matter (SOM) (Freundlich sorption coefficient, : 346-979 mg L kg; 1/: 0.62-0.76) but decreased with increasing soil pH due to a decreasing fraction of the cationic species. Sorption of SMX and sorption hysteresis were stronger in the nonirrigated soil (: 4.14 mg L kg ± 0.02; 1/: 0.69 ± 0.02) than in the irrigated soils (: 0.65-1.38 mg L kg; 1/: 0.68-0.75). Irrigation (e.g., competition with SMX accumulated in soil or with other organic compounds contained in wastewater) and SOM quality (i.e., increase of carboxylic moieties with increasing time of irrigation) had a stronger effect on SMX sorption and its hysteresis than soil organic carbon content. Whereas sorption of SMX can be reduced by long-term irrigation with wastewater, sorption of CIP is intense also after prolonged irrigation.

RESUMO

Irrigation with wastewater releases pharmaceuticals, pathogenic bacteria, and resistance genes, but little is known about the accumulation of these contaminants in the environment when wastewater is applied for decades. We sampled a chronosequence of soils that were variously irrigated with wastewater from zero up to 100 years in the Mezquital Valley, Mexico, and investigated the accumulation of ciprofloxacin, enrofloxacin, sulfamethoxazole, trimethoprim, clarithromycin, carbamazepine, bezafibrate, naproxen, diclofenac, as well as the occurrence of Enterococcus spp., and sul and qnr resistance genes. Total concentrations of ciprofloxacin, sulfamethoxazole, and carbamazepine increased with irrigation duration reaching 95% of their upper limit of 1.4 µg/kg (ciprofloxacin), 4.3 µg/kg (sulfamethoxazole), and 5.4 µg/kg (carbamazepine) in soils irrigated for 19-28 years. Accumulation was soil-type-specific, with largest accumulation rates in Leptosols and no time-trend in Vertisols. Acidic pharmaceuticals (diclofenac, naproxen, bezafibrate) were not retained and thus did not accumulate in soils. We did not detect qnrA genes, but qnrS and qnrB genes were found in two of the irrigated soils. Relative concentrations of sul1 genes in irrigated soils were two orders of magnitude larger (3.15 × 10(-3) ± 0.22 × 10(-3) copies/16S rDNA) than in non-irrigated soils (4.35 × 10(-5)± 1.00 × 10(-5) copies/16S rDNA), while those of sul2 exceeded the ones in non-irrigated soils still by a factor of 22 (6.61 × 10(-4) ± 0.59 × 10(-4) versus 2.99 × 10(-5) ± 0.26 × 10(-5) copies/16S rDNA). Absolute numbers of sul genes continued to increase with prolonging irrigation together with Enterococcus spp. 23S rDNA and total 16S rDNA contents. Increasing total concentrations of antibiotics in soil are not accompanied by increasing relative abundances of resistance genes. Nevertheless, wastewater irrigation enlarges the absolute concentration of resistance genes in soils due to a long-term increase in total microbial biomass.

Assuntos

RESUMO

The irrigation or agricultural land with wastewater is increasingly practiced in many parts of the world as a consequence of growing populations and urbanization. The risks emerging from pharmaceuticals that are contained in wastewater for soils and groundwater have hardly been investigated. We studied leaching and effects of naproxen, ibuprofen, bezafibrate, diclofenac, gemfibrocil, clarithromycin, trimethoprim, clindamycin, erythromycin, and metoprolol in a soil column experiment simulating an irrigation event with 8.6 cm of wastewater containing 20 microg L(-1) or 2000 microg L(-1) of each compound or of erythromycin alone. The leached fraction of applied pharmaceuticals ranged from 0.1 +/- 0.1% (clarithromycin, 2000 microg L(-1)) to 130 +/- 41% (naproxen, 20 microg L(-1)) and tended to increase with decreasing K(d) or K(oc). Naproxen transport was similar to that of the tracer chloride. Ibuprofen was also hardly retarded (R = 1.20 +/- 0.18), but showed a higher degradation rate of 0.02 +/- 0.004 h(-1) (2000 microg L(-1)) than naproxen. The transport of a pulse of 2000 microg L(-1) of bezafibrate could be described with a retardation factor of 1.5 and a degradation rate of 0.033 h(-1). The application of erythromycin alone or of a cocktail of all pharmaceuticals significantly increased soil CO2 emissions by 50% 1 d after the application. There is a considerable risk that pharmaceuticals are leached to groundwater during wastewater irrigation.

Assuntos