Scientific concepts and methods for moving persistence assessments into the 21st century.

The evaluation of a chemical substance's persistence is key to understanding its environmental fate, exposure concentration, and, ultimately, environmental risk. Traditional biodegradation test methods were developed many years ago for soluble, nonvolatile, single-constituent test substances, which do not represent the wide range of manufactured chemical substances. In addition, the Organisation for Economic Co-operation and Development (OECD) screening and simulation test methods do not fully reflect the environmental conditions into which substances are released and, therefore, estimates of chemical degradation half-lives can be very uncertain and may misrepresent real environmental processes. In this paper, we address the challenges and limitations facing current test methods and the scientific advances that are helping to both understand and provide solutions to them. Some of these advancements include the following: (1) robust methods that provide a deeper understanding of microbial composition, diversity, and abundance to ensure consistency and/or interpret variability between tests; (2) benchmarking tools and reference substances that aid in persistence evaluations through comparison against substances with well-quantified degradation profiles; (3) analytical methods that allow quantification for parent and metabolites at environmentally relevant concentrations, and inform on test substance bioavailability, biochemical pathways, rates of primary versus overall degradation, and rates of metabolite formation and decay; (4) modeling tools that predict the likelihood of microbial biotransformation, as well as biochemical pathways; and (5) modeling approaches that allow for derivation of more generally applicable biotransformation rate constants, by accounting for physical and/or chemical processes and test system design when evaluating test data. We also identify that, while such advancements could improve the certainty and accuracy of persistence assessments, the mechanisms and processes by which they are translated into regulatory practice and development of new OECD test guidelines need improving and accelerating. Where uncertainty remains, holistic weight of evidence approaches may be required to accurately assess the persistence of chemicals. Integr Environ Assess Manag 2022;18:1454-1487. © 2022 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

What is the spatial-temporal behavior of a low, medium and high adsorptive compound in two contrasting natural sediments in OECD 218/219 test systems?

Artificial sediment used in studies according to OECD 218/219 (Sediment Water Chironomid Toxicity Test Using Spiked Sediment/Water) does not necessarily mirror the characteristics of natural sediments. To investigate the influence of sediment characteristics on the spatial-temporal behaviors of bixafen (KfOM = 2244 mL/g), fluopyram (KfOM = 162 mL/g) and N,N-dimethylsulfamide (KfOM ≈ 0 mL/g), experiments according to OECD 218/219 with two contrasting natural sediments were conducted. The silt loam sediment provided a high content of organic matter (OM) (13.1%), while the OM (0.45%) of the sandy sediment was low. Diffusion into (OECD 219) or out (OECD 218) of the sediment was dependent on the extent of adsorption, which is linked to the model compounds ́ adsorption affinities and the sediments ́ OM. Consequently, N,N-dimethylsulfamide showed unhindered mobility in each experimental set up, while the high adsorption affinities of fluopyram and bixafen limited the diffusion in the respective sediments. Therefore, in experiments with the silt loam sediment, both compounds revealed a limited mobility and either accumulated in the top 5 mm of the sediment (OECD 219) or remained homogenously distributed over the sediment depth (OECD 218). A greater mobility was observed within the sandy sediment.The influence of OM as found in a study using artificial sediment could be confirmed. Moreover, the applicability of a TOXSWA model was reassured to predict the measured concentrations at different sediment depths. TOXSWA is used in the regulatory exposure assessment to simulate the behavior of pesticides in surface waters. Calibration of three driving input parameters by inverse modelling (diffusion-, adsorption coefficient and OM) revealed no potential for improvement. The core sampling technique used and the model may contribute to a more realistic determination of concentration to which the Chironomid larvae are exposed to. This applies to water sediment test systems where the test organisms do not evenly inhabit the sediment.

What is the actual exposure of organic compounds on Chironomus riparius? - A novel methodology enabling the depth-related analysis in sediment microcosms.

A novel active sampling method enabled determination of sediment depth profiles revealing the spatial distribution of model compounds N,N-dimethylsulfamide, fluopyram and bixafen (low, medium, high adsorption affinity) in sediment microcosms according to OECD Test 218/219 (Sediment-Water Chironomid Toxicity Test Using Spiked Sediment/Spiked Water). After the overlying water was removed, plastic tubes were inserted into the sediment and the microcosms were frozen. For depth-related analysis, each "sediment core" was mounted in a cutting device and sawed into three 5-mm-slices, respectively (top, middle, bottom). Each slice was centrifuged for sediment and pore water separation. By various sampling dates within 28 days, we could follow the behavior of model compounds depending on sorption affinities and display specific distribution patterns within the sediment. N,N-dimethylsulfamide showing no sediment adsorption, migrated unhindered in (OECD 219) and out (OECD 218) of the sediment via pore water, resulting in homogenous distributions in both test designs. Fluopyram with moderate adsorption affinity revealed a concentration gradient with declining amounts from top to bottom layer (OECD 219) and higher amounts in the middle and bottom layer as compared to the top layer (OECD 218). Bixafen providing a strong adsorption affinity accumulated in the top layer in OECD 219, while no concentration gradients became visible in OECD 218. For establishing a Toxic Substances in Surface Waters (TOXSWA) model, we compared our measurements with simulated results revealing good agreements. The presented methodology is a useful tool to determine more realistic sediment and pore water concentrations, which the Chironomid larvae are exposed to.

Does long-term irrigation with untreated wastewater accelerate the dissipation of pharmaceuticals in soil?

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.

Release of Pharmaceuticals under Reducing Conditions in a Wastewater-Irrigated Mexican Soil.

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.

Long-term Wastewater Irrigation Reduces Sulfamethoxazole Sorption, but Not Ciprofloxacin Binding, in Mexican Soils.

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.

Accumulation of pharmaceuticals, Enterococcus, and resistance genes in soils irrigated with wastewater for zero to 100 years in central Mexico.

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.

Aging of methabenzthiazuron, imidacloprid, and N,N-dimethylsulfamide in silty soils and effects on sorption and dissipation.

Differences in soil properties can influence the fate of plant protection agents in the environment. The present study aims to investigate the sorption behavior and related aging processes of imidacloprid (IMI; insecticide), methabenzthiazuron (MBT; herbicide), and N,N-dimethylsulfamide (DMSA; degradate of the fungicide tolylfluanid) in six soils of silty texture but otherwise varying properties. The sorption behavior of these ¹4C-labeled compounds exhibiting different physicochemical properties was characterized by applying a three-step sequential extraction procedure. After 119 d, MBT revealed strongest sorption (K'(tot) 47.4-200.4 L/kg), followed by IMI (K'(tot) 11.7-30.6 L/kg), and DMSA with K'(tot) close to zero. Aged sorption factors (AFs) were calculated to characterize aging processes over time exhibiting a 2.6-3.5-fold (IMI), a 1.8-4.5-fold (MBT), and no (DMSA) increase of sorbed amounts within 84 d. Sorption and aging varied widely in the group of silty soils, which differed with respect to organic matter content, C/N-ratio, and microbial soil parameters. The time-dependent increase of adsorption of MBT and IMI was more pronounced in those soils that had a lower organic carbon and low microbial biomass content. Concomitantly, MBT and IMI degradation decelerated, presumably because of aged sorption at inner binding sites leading to a lower accessibility. In contrast, in the soils with a higher organic carbon content a strong initial (but later still reversible) sorption of MBT and IMI, occurring presumably at outer surface sites, reduced the extent of time-dependent diffusion toward inner binding sites.