Exposure and Transport of Alkaloids and Phytoestrogens from Soybeans to Agricultural Soils and Streams in the Midwestern United States.

Phytotoxins are naturally produced toxins with potencies similar/higher than many anthropogenic micropollutants. Nevertheless, little is known regarding their environmental fate and off-field transport to streams. To fill this research gap, a network of six basins in the Midwestern United States with substantial soybean production was selected for the study. Stream water (n = 110), soybean plant tissues (n = 8), and soil samples (n = 16) were analyzed for 12 phytotoxins (5 alkaloids and 7 phytoestrogens) and 2 widely used herbicides (atrazine and metolachlor). Overall, at least 1 phytotoxin was detected in 82% of the samples, with as many as 11 phytotoxins detected in a single sample (median = 5), with a concentration range from below detection to 37 and 68 ng/L for alkaloids and phytoestrogens, respectively. In contrast, the herbicides were ubiquitously detected at substantially higher concentrations (atrazine: 99% and metolachlor: 83%; the concentrations range from below detection to 150 and 410 ng/L, respectively). There was an apparent seasonal pattern for phytotoxins, where occurrence prior to and during harvest season (September to November) and during the snow melt season (March) was higher than that in December-January. Runoff events increased phytotoxin and herbicide concentrations compared to those in base-flow conditions. Phytotoxin plant concentrations were orders of magnitude higher compared to those measured in soil and streams. These results demonstrate the potential exposure of aquatic and terrestrial organisms to soybean-derived phytotoxins.

Linking Morphology, Toxicokinetic, and Toxicodynamic Traits of Aquatic Invertebrates to Pyrethroid Sensitivity.

Pyrethroid insecticides are known to be highly toxic to most aquatic nontarget organisms, but little is known about the mechanisms causing some species to be highly sensitive while others are hardly affected by the pyrethroids. The aim of the present study was to measure the sensitivity (EC50-values) of 10 aquatic invertebrates toward a 24 h pulse of the pyrethroid cypermethrin and subsequently test if the difference in sensitivity could be explained by measured morphological and physiological traits and modeled toxicokinetic (TK) and toxicodynamic (TD) parameters. Large differences were observed for the measured uptake and elimination kinetics, with bioconcentration factors (BCFs) ranging from 53 to 2337 at the end of the exposure. Similarly, large differences were observed for the TDs, and EC50-values after 168 h varied 120-fold. Modeling the whole organism cypermethrin concentrations indicated compartmentation into a sorbed fraction and two internal fractions: a bioavailable and non-bioavailable internal fraction. Strong correlations between surface/volume area and the TK parameters (sorption and uptake rate constants and the resulting BCF) were found, but none of the TK parameters correlated with sensitivity. The only parameter consistently correlating with sensitivity across all species was the killing rate constant of the GUTS-RED-SD model (the reduced general unified threshold models of survival assuming stochastic death), indicating that sensitivity toward cypermethrin is more related to the TD parameters than to TK parameters.

Nitrate leaching and nitrous oxide emissions from maize after grass-clover on a coarse sandy soil: Mitigation potentials of 3,4-dimethylpyrazole phosphate (DMPP).

Cropping of maize (Zea mays L.) on sandy soil in wet climates involves a significant risk for nitrogen (N) losses, since nitrate added in fertilizers or produced from residues and manure may be lost outside the period with active crop N uptake. This one-year lysimeter experiment investigated the potential of Vizura®, a formulation for liquid manure (slurry) with the nitrification inhibitor 3,4-dimethylpyrazole phosphate (DMPP), to mitigate nitrous oxide (N2O) emissions and nitrate (NO3-) leaching from a coarse sandy soil cropped with maize. Maize followed grass-clover (Lolium perenne L.-Trifolium pratense L.) with spring incorporation and was fertilised with cattle slurry. A total of 12 treatments in triplicate were included in a factorial experiment with 1 m2 large and 1.4 m deep lysimeters: 1) with or without spraying the above-ground biomass of grass-clover with DMPP before incorporation; 2) application of cattle manure with or without DMPP, or no fertilization; and 3) natural rainfall or extra rain events to represent wet spring conditions, which were simulated with an automated and programmable irrigation system. Around 20 kg N ha-1 was returned to the soil in grass-clover above-ground biomass, and 145 kg N ha-1 in cattle manure. Cumulative annual N2O emissions ranged from 0.4 to 1.3 kg N ha-1, with between 49 and 86% of emissions occurring during spring. Manure application increased N2O emissions, while extra rainfall had no effect. The mitigation of N2O emissions by DMPP ranged from 46 to 67% under natural, and from 44 to 48% under high rainfall conditions. Total annual NO3- leaching ranged from 65 to 162 kg N ha-1. The extent of NO3- leaching to 1.4 m depth during spring was low, and instead most (72-83%) of total annual NO3--N leaching was recorded during autumn before harvest. The extra rainfall during spring increased NO3--N leaching in the pre-harvest period, but it is not clear to what extent this was associated with the N in grass-clover residues or manure applied in spring, or from N mineralisation below the root zone. Despite evidence for a reduction of NO3- leaching in three of four scenarios, overall this effect was not significant. No DMPP was detected in leachates. In conclusion, DMPP significantly reduced N2O emissions from cattle manure on this sandy loam soil independent of rainfall, while there was no significant effect on NO3- leaching. The results indicate that N2O emissions and NO3--N leaching were partly derived from below-ground sources of N not affected by DMPP, which should be further investigated to better predict the mitigation potential of nitrification inhibitors.

Comprehensive Study of Organic Micro-pollutants in Flooded Paddy Soils in Central Vietnam: Levels, Pollution Pathways and Sources.

In order to assess the environmental impacts caused by flood to the paddy field, 940 semi-volatile organic compounds (SVOCs) were screened in paddy soil samples taken in central Vietnam before and after flooding. The concentration of 166 SVOCs in soil samples ranged from 0.031 to 2241 (mean 89.1) µg kg-1 dry wt. Chemicals originating from household sources showed the highest level, followed by chemicals originating from agriculture. Since untreated domestic wastewater used for agricultural irrigation, organic micro-pollutants in domestic wastewater is the main source of pollutants in paddy soil. However, contamination levels of pollutants in paddy soil after flooding were lower than those before flooding, possibly due to the removal of pollutants by floodwater. As a result, pollution characteristic of pollutants at sampling locations were different before flooding while they became similar after flooding due to the dispersion and elution of organic pollutants from soil into floodwaters.

Amino Acid-Assisted Dehalogenation of Carbon Tetrachloride by Green Rust: Inhibition of Chloroform Production.

Layered FeII-FeIII hydroxides (green rusts, GRs) are promising reactants for reductive dechlorination of chlorinated solvents due to high reaction rates and the opportunity to inject reactive slurries of the compounds into contaminant plumes. However, it is necessary to develop strategies that reduce the formation of toxic byproducts such as chloroform (CF). In this study, carbon tetrachloride (CT) dehalogenation by the chloride form of GR (GRCl) was tested in the presence of glycine (GLY) and other selected amino acids. GLY, alanine (ALA), and serine (SER) all resulted in remarkable suppression of CF formation with only ∼10% of CF recovery while sarcosine (SAR) showed insignificant effects. For two nonamino acid buffers, TRIS had little effect while HEPES resulted in a 40 times lower rate constant compared to experiments in which no buffer was added. The FeII complexing properties of the amino acids and buffers caused variable extents of GRCl dissolution which was linearly correlated with CF suppression and dehalogenation rate. We hypothesize that the CF suppression seen for amino acids is caused by stabilization of carbene intermediates via the carbonyl group. Different effects on CF suppression and CT dehalogenation rate were expected because of the different structural and chemical properties of the amino acids.

UPLC-MS/MS determination of ptaquiloside and pterosin B in preserved natural water.

The naturally occurring carcinogen ptaquiloside and its degradation product pterosin B are found in water leaching from bracken stands. The objective of this work is to present a new sample preservation method and a fast UPLC-MS/MS method for quantification of ptaquiloside and pterosin B in environmental water samples, employing a novel internal standard. A faster, reliable, and efficient method was developed for isolation of high purity ptaquiloside and pterosin B from plant material for use as analytical standards, with purity verified by 1H-NMR. The chemical analysis was performed by cleanup and preconcentration of samples with solid phase extraction, before analyte quantification with UPLC-MS/MS. By including gradient elution and optimizing the liquid chromatography mobile phase buffer system, a total run cycle of 5 min was achieved, with method detection limits, including preconcentration, of 8 and 4 ng/L for ptaquiloside and pterosin B, respectively. The use of loganin as internal standard improved repeatability of the determination of both analytes, though it could not be employed for sample preparation. Buffering raw water samples in situ with ammonium acetate to pH ∼5.5 decisively increased sample integrity at realistic transportation and storing conditions prior to extraction. Groundwater samples collected in November 2015 at the shallow water table below a Danish bracken stand were preserved and analyzed using the above methods, and PTA concentrations of 3.8 ± 0.24 µg/L (±sd, n = 3) were found, much higher than previously reported. Graphical abstract Workflow overview of ptaquiloside determination.

Land management of bracken needs to account for bracken carcinogens--a case study from Britain.

Bracken ferns are some of the most widespread ferns in the World causing immense problems for land managers, foresters and rangers. Bracken is suspected of causing cancer in Humans due to its content of the carcinogen ptaquiloside. Ingestion of bracken, or food and drinking water contaminated with ptaquiloside may be the cause. The aim of this study was to monitor the content of ptaquiloside in 20 bracken stands from Britain to obtain a better understanding of the ptaquiloside dynamics and to evaluate the environmental implications of using different cutting regimes in bracken management. The ptaquiloside content in fronds ranged between 50 and 5790 µg/g corresponding to a ptaquiloside load in the standing biomass of up to 590 mg/m(2) in mature fronds. Ptaquiloside was also found in the underground rhizome system (11-657 µg/g) and in decaying litter (0.1-5.8 µg/g). The amount of ptaquiloside present in bracken stands at any given time is difficult to predict and did not show any correlations with edaphic growth factors. The content of ptaquiloside turned out to be higher in fronds emerging after cutting compared to uncut fronds. Environmental risk assessment and bracken management must therefore be based on actual and site specific determinations of the ptaquiloside content. Care must be taken to avoid leaching from cut ferns to aquifers and other recipients and appropriate precautionary measures must be taken to protect staff from exposure to bracken dust.

Determination of sulfadiazine in phosphate- and DOC-rich agricultural drainage water using solid-phase extraction followed by liquid chromatography-tandem mass spectrometry.

Trace levels of the veterinary antibiotic compound sulfadiazine (SDZ) can be determined in agricultural drainage water samples with this new method. Optimized sample pretreatment and solid-phase extraction was combined with liquid chromatography coupled to tandem mass spectrometry (SPE LC-MS/MS) using positive electrospray ionization. The linear dynamic range for the LC-MS/MS was assessed from 5 µg/L to 25 mg/L with a 15-point calibration curve displaying a coefficient of correlation r(2) = 0.9915. Agricultural drainage water spiked at a concentration of 25 ng/L gave recoveries between 63 and 98 % (relative standard deviation 15 %), while at 10 ng/L, it showed a lower recovery of 32 % (relative standard deviation 47 %). The final SPE LC-MS/MS method had a limit of detection (LOD)(Method) and a limit of quantification (LOQ)(Method) of 7.5 and 23 ng/L agricultural drainage water, respectively. Determination of SDZ, spiked at a realistic concentration of 50 µg/L, in artificial drainage water (ADW) containing common and high levels of phosphate (0.05, 0.5, and 5 mg/L) gave recoveries between 70 and 92 % (relative standard deviation 7.4-12.9 %). Analysis of the same realistic concentration of SDZ in ADW, spiked with common and high levels of dissolved organic carbon (2, 6, and 15 mg/L) confirmed the possible adaptation of a tandem solid-phase extraction (strong anion exchange (SAX)-hydrophilic-lipophilic balance (HLB)) followed by liquid chromatography-tandem mass spectrometry methodology. Recoveries obtained ranged from 104 to 109 % (relative standard deviation 2.8-5.2 %). The new methods enable determination of the veterinary antibiotic compound SDZ in agricultural drainage water from field experiments and monitoring schemes for phosphate- and dissolved organic carbon (DOC)-rich water samples in intensive farming areas.

Ageing of atrazine in manure amended soils assessed by bioavailability to Pseudomonas sp. strain ADP.

Animal manure is applied to agricultural land in areas of high livestock production. In the present study, we evaluated ageing of atrazine in two topsoils with and without addition of manure and in one subsoil. Ageing was assessed as the bioavailability of atrazine to the atrazine mineralizing bacteria Pseudomonas sp. strain ADP. Throughout an ageing period of 90 days bioavailability was investigated at days 1, 10, 32, 60 and 90, where ~10(8) cells g(-1) of the ADP strain was inoculated to the (14)C-atrazine exposed soil and (14)CO2 was collected over 7 days as a measure of mineralized atrazine. Even though the bioavailable residue decreased in all of the three soils as time proceeded, we found that ageing occurred faster in the topsoils rich in organic carbon than in subsoil. For one topsoil rich in organic carbon content, Simmelkær, we observed a higher degree of ageing when treated with manure. Contrarily, sorption experiments showed less sorption to Simmelkær treated with manure than the untreated soil indicating that sorption processes are not the only mechanisms of ageing. The other topsoil low in organic carbon content, Ringe, showed no significant difference in ageing between the manure-treated and untreated soil. The present study illustrates that not simply the organic carbon content influences adsorption and ageing of atrazine in soil but the origin and composition of organic matter plays an important role.

Adsorption of the disinfectant benzalkonium chloride on montmorillonite. Synergistic effect in mixture of molecules with different chain lengths.

The biocide benzalkonium chloride (BAC) is a mix of cationic alkylbenzyldimethylammonium surfactants having different alkyl chain lengths. A comparative study of adsorption on the phyllosilicate clay montmorillonite of two of these surfactants, with alkyl chains having respectively 12 C atoms (BAC-12) and 14 C atoms (BAC-14), and a mixture of both surfactants is presented in this work. Adsorption isotherms were performed for individual surfactants and for a 1:1 mixture BAC-12+BAC-14. The adsorption was investigated in an ample concentration range that covers almost seven orders of magnitude in concentrations (from 1 nM to 10 mM), range that includes environmentally relevant concentrations. Quantification of BAC was performed by HPLC-UV and LC-MS and the results were completed with powder X-Ray diffraction. The adsorption of both surfactants leads to adsorption isotherms with two well differentiated steps. The first step corresponds almost exclusively to a cation exchange process, and the binding constant is very similar for both surfactants. The second step of the isotherms is observed at higher concentrations and adsorption is mainly driven by lateral interactions between surfactant molecules. The binding constant of this step is larger for BAC-14 than for BAC-12. Adsorption from a BAC-12+BAC-14 mixture shows a synergistic behaviour, possibly due to a better packing arrangement in the interlayer. Calculations show that in natural systems silicate clays are major sorbents of BAC at low concentrations whereas binding to humic acid is predominant at high concentrations.

Modeling of phenoxy acid herbicide mineralization and growth of microbial degraders in 15 soils monitored by quantitative real-time PCR of the functional tfdA gene.

Mineralization potentials, rates, and kinetics of the three phenoxy acid (PA) herbicides, 2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA), and 2-(4-chloro-2-methylphenoxy)propanoic acid (MCPP), were investigated and compared in 15 soils collected from five continents. The mineralization patterns were fitted by zero/linear or exponential growth forms of the three-half-order models and by logarithmic (log), first-order, or zero-order kinetic models. Prior and subsequent to the mineralization event, tfdA genes were quantified using real-time PCR to estimate the genetic potential for degrading PA in the soils. In 25 of the 45 mineralization scenarios, ∼60% mineralization was observed within 118 days. Elevated concentrations of tfdA in the range 1 × 10(5) to 5 × 10(7) gene copies g(-1) of soil were observed in soils where mineralization could be described by using growth-linked kinetic models. A clear trend was observed that the mineralization rates of the three PAs occurred in the order 2,4-D > MCPA > MCPP, and a correlation was observed between rapid mineralization and soils exposed to PA previously. Finally, for 2,4-D mineralization, all seven mineralization patterns which were best fitted by the exponential model yielded a higher tfdA gene potential after mineralization had occurred than the three mineralization patterns best fitted by the Lin model.

Indole and quinolizidine alkaloids from blue lupin leach to agricultural drainage water.

Phytotoxins are produced in plants including agricultural crops. Lupins and other plants of the Fabaceae family produce toxic alkaloids. These alkaloids have been studied in food and feed, however, the environmental fate of alkaloids produced by cultivated lupins is largely unknown. Therefore, we conducted an agricultural field experiment to investigate the occurrence of indole and quinolizidine alkaloids in lupin plant tissues, soil, soil pore water and in drainage water. During the field experiment, alkaloids were regularly quantified (median concentrations) in lupin (13-8.7 × 103 ng/g dry weight (dw)), and topsoils at depth 0-5 cm (0.1-10 ng/g dw), and depth 15-30 cm (0.2-8.5 ng/g dw), soil pore water (0.2-7.5 ng/L) and drainage water samples (0.4-18 ng/L). Lupanine was the dominant alkaloid in all collected samples. Cumulative amounts of alkaloids emitted via drainage water were around 0.1-11 mg/ha for individual alkaloids over one growing season. The total cumulative amount of alkaloid in drainage water was 14 mg/ha, which is a very small amount compared to the mass of alkaloid in the lupin biomass (11 kg/ha) and soil (0.02 kg/ha). Nearly half of the alkaloids were exported in the drainage water during high flow events, indicating that alkaloids transport preferentially via macropores. These findings indicate that drainage from lupin cultivated areas contribute to surface water contamination. The environmental and ecotoxicological relevance of alkaloids as newly identified aquatic micropollutants in areas with agricultural activities have yet to be assessed.

Fast peroxydisulfate oxidation of the antibiotic norfloxacin catalyzed by cyanobacterial biochar.

Peroxydisulfate (PDS) is a common oxidant for organic contaminant remediation. PDS is typically activated by metal catalysts to generate reactive radicals. Unfortunately, as radicals are non-selective and metal catalysts may cause secondary contamination, alternative selective non-radical pathways and non-metal catalysts need attention. Here we investigated PDS oxidation of commonly detected antibiotic Norfloxacin (NOR) using cyanobacterial nitrogen rich biochars (CBs) as catalysts. NOR was fully degraded by CB pyrolysed at 950 °C (CB950) within 120 min. CB950 caused threefold faster degradation than low pyrolysis temperature (PT) CBs and achieved a maximum surface area normalized rate constant of 4.38 × 10-2 min-1 m-2 L compared to widely used metal catalysts. CB950 maintained full reactivity after four repeated uses. High defluorination (82%) and mineralization (>82%) were observed for CB950/PDS. CBs were active over a broad pH range (3-10), but with twice as high rates under alkaline compared with neutral conditions. NOR is degraded by organic, •OH and SO4•- radicals in low PT CBs/PDS systems, where the presence of MnII promotes radical generation. Electron transfer reactions with radicals supplemented dominate high PT CBs/PDS systems. This study demonstrates high PT biochars from algal bloom biomass may find use as catalysts for organic contaminant oxidation.

Occurrence of pyrrolizidine alkaloids in ragwort plants, soils and surface waters at the field scale in grassland.

Pyrrolizidine alkaloids (PA)s are natural toxins produced by a variety of plants including ragwort. The PAs present a serious health risk to human and livestock. Although these compounds have been extensively studied in food and feed, little is known regarding their environmental fate. To fill this data gap, we investigated the occurrence of PAs in ragwort plants, soils and surface waters at three locations where ragwort was the dominant plant species to better understand their environmental distribution. The concentrations of PAs were quantified during the full growing season (April-November) and assessed in relation to rain events. PA concentrations ranged from 3.2-6.6 g/kg dry weight (dw) in plants, 0.8-4.0 mg/kg dw in soils, and 6.0-529 µg/L in surface waters. Maximum PA concentrations in the soil (4 mg/kg) and water (529 µg/L) were in mid-May just before flowering. The average distribution of PAs in water was approximately 5 g/10,000 L, compared to the average amounts present in ragwort (506 kg/ha), and soil (1.7 kg/ha). In general, concentrations of PAs increase in the soil and surface water following rain events.

Impacts of wastewater treatment plant upgrades on the distribution and risks of pharmaceuticals in receiving rivers.

Upgrades of wastewater treatment plant (WWTP) and full-scale application of additional advanced oxidation processes have been proven to be effective in reducing the nutrient emissions to the environment; however, the impacts of WWTP upgrades on the receiving waters with regard to the occurrence and ecological risks of pharmaceuticals are still unclear. In this study, 27 pharmaceuticals with diverse physicochemical properties were monitored in four rivers in Beijing, each of which was heavily impacted by a large-scale WWTP. Three-year sampling campaigns were conducted, covering the periods before and after the WWTP upgrades. The results show that the newly added combined treatment processes (e.g., biological filter, ultrafiltration, ozonation, and NaClO disinfection) reduced the total pharmaceutical concentrations in the effluents by 45-74%. The composition profiles reveal that the upgrades of two studied WWTPs resulted in a significant reduction of pharmaceutical concentrations in the receiving rivers, while little impacts were observed for the other rivers. The risk assessment shows that the acute toxic pressures in the studied rivers were generally low and the WWTP upgrades were conducive to reduce the risks for most of pharmaceuticals. However, erythromycin and ofloxacin still posed high risk, indicating the potential adverse effect of pharmaceuticals on aquatic environment.

Heavy metal contents, mobility and origin in agricultural topsoils of the Galápagos Islands.

While the Galápagos Islands have been renowned for their unique flora and fauna since the time of Charles Darwin, the soils of the isolated island chain have been mostly overlooked and little information on their heavy metal contents is available. The aim of this study was therefore to examine the total heavy metal (Cd, Co, Cr, Cu, Ni, Pb, U, Zn) contents of soils from the agricultural areas on islands Isabela, Santa Cruz and San Cristóbal, and identify trends with duration of exposure to weathering processes. Additionally, the mobility of these elements was assessed using ammonium nitrate extraction. In general, levels of Cd, Co, Cr, Cu, Ni and Zn were high compared to other world locations, while Pb levels were low and U levels were similar. Ni, Co, Cr, and to a lesser extent Pb and U tended to accumulate with increasing weathering duration. Soil concentrations of Cd, Zn, Cu, and possibly Pb and U, may have been influenced by use of agrochemicals, particularly on Santa Cruz Island. Mobility of Cd displayed an increasing trend with soil age, while Ni mobility decreased. Many soils had total contents of Cd, Co, Cr, Cu, Ni and Zn above threshold values indicating possible ecological or health risks. Systematic examination of trace element contents in soils from pristine national park areas would further assist in the delineation of background levels and the development of soil quality standards to ensure crop quality, animal and human health on this unique island chain.

Biochar catalyzed dechlorination - Which biochar properties matter?

Bone char catalyzed dechlorination of trichloroethylene (TCE) by green rust (iron(II)-iron(III) hydroxide, GR) has introduced a promising new reaction platform for degradation of chlorinated solvents. This study aimed to reveal whether a broader class of biochars are catalytically active for the dechlorination reaction and to identify which biochar properties are the most important for the catalytic activity. Biochars produced by pyrolysis of animal, plant, and sewage waste substrates at 950 °C were prepared for catalytic dechlorination of TCE by GR tested in batch experiments with 0.15 g L-1 biochar, 3.2 g L-1 GR, and ~ 20 µM TCE. The results showed that the biochar substrate significantly affects its catalytic activity, with the highest TCE reduction rate observed for bone and shrimp-based biochars (k ≥ 0.18 h-1), whereas no reactivity was seen for graphite and activated carbon references. Multivariate regression indicated that the biochar catalytic activity is controlled by multiple biochar properties - biochar surface area, TCE sorption, abundance of C-O groups, and pore size are the properties that impact the catalytic activity most. Derivation of biochar reactivity relationship for a broad spectrum of biochars provides a new approach for identifying proper biochar catalysts for pollutant degradation.

Removal of phytotoxins in filter sand used for drinking water treatment.

Phytotoxins - toxins produced by plants - are contaminants with the potential to impair drinking water quality. They encompass a large group of toxic, partially persistent compounds that have been detected in seepage waters and in shallow wells used for drinking water production. If phytotoxins enter wells used for drinking water production, it is essential to know if the drinking water treatment processes will remove them from the water phase. However, it is currently unknown whether phytotoxins remain stable during traditional groundwater treatment using sand filters as the main treatment process. The objective of this study is to investigate removal potential of phytotoxins in biological sand filters and to asses if the removal potential is similar at different waterworks. Microcosms were set up with filter sand and drinking water collected at different groundwater-based waterworks. To be able to monitor phytotoxin removal ptaquiloside, caudatoside, gramine, sparteine, jacobine N-oxide, senecionine N-oxide and caffeine were applied at initial concentrations of 300 µg L-1, which is approx. two orders of magnitude higher than currently detected in environment, but expected to cover extreme environmental conditions. Removal was monitored over a period of 14 days. Despite the high initial concentration, all filter sands removed ptaquiloside and caudatoside completely from the water phase and at waterworks where pellet softening was implemented (pH 8.4) prior to rapid sand filtration, complete removal occurred within the first 30 min. All filter sands removed gramine and sparteine, primarily by a biological process, while jacobine N-oxide, senecionine N-oxide and caffeine were recalcitrant in the filter sands. During degradation of ptaquiloside and caudatoside we observed formation and subsequent removal of degradation products pterosin B and A. Filter sands with the highest removal potential were characterised by high contents of deposited iron and manganese oxides and hence large specific surface areas. Difference between bacterial communities investigated by 16S rRNA gene analyses did not explain different removal in the filter sands. All five investigated filter sands showed similar degradation patterns regardless of water chemistry and waterworks of origin. In drinking water treatment systems biological sand filters might therefore remove phytotoxin contaminants such as ptaquiloside, caudatoside, gramine, sparteine, while for other compounds e.g. jacobine N-oxide, senecionine N-oxide further investigations involving more advanced treatment options are needed.

Occurrence, source estimation and risk assessment of pharmaceuticals in the Chaobai River characterized by adjacent land use.

This study investigated the occurrence of 27 pharmaceuticals with diverse physicochemical properties in a year-long monitoring campaign in the Chaobai River, China. The correlation between the distribution of pharmaceuticals in the river and the adjacent sources was elucidated. The results indicate that the agriculture area was the most polluted area with a median summed pharmaceutical concentration of 225.3 ng L-1, followed by the urban area and the mountain area with the corresponding values of 136.9 and 29.9 ng L-1, respectively. In terms of individual compounds, 22 out of 27 compounds were detected with concentrations ranging from <1 to 1972 ng L-1. Caffeine, carbamazepine, azithromycin, bezafibrate, metoprolol, sulfadiazine, sulfamethoxazole, clarithromycin, erythromycin, roxithromycin, and trimethoprim were pharmaceuticals with relatively high levels, with median concentrations ranging from 3.3 to 25.6 ng L-1 and detection frequencies ranging from 40% to 97%. Higher concentrations were mainly observed during cold seasons, with mean concentrations 1 to 52 times as high as those during warm seasons. Spatial analysis reveals that the pharmaceutical concentrations in different areas were impacted by different sources. A wastewater treatment plant was an important source in the urban area, while the agriculture area was impacted by various treated and untreated wastewater sources. The species sensitivity distribution model and risk quotient (RQ) method were combined in the ecological risk assessment. The results indicate that the multi-substance potentially affected fraction (msPAF) values of the sampling sites were below 0.04%, whereas nearly half of RQ values were higher than 1. Caffeine was proposed as a priority compound due to its high contribution rate (i.e., 79%) to the cumulative msPAF value, which implies that increased control and management of untreated wastewater sources along the Chaobai River is necessary.

The invasive butterbur contaminates stream and seepage water in groundwater wells with toxic pyrrolizidine alkaloids.

Pyrrolizidine alkaloids (PAs) are persistent mutagenic and carcinogenic compounds produced by many common plant species. Health authorities recommend minimising human exposure via food and medicinal products to ensure consumer health and safety. However, there is little awareness that PAs can contaminate water resources. Therefore, no regulations exist to limit PAs in drinking water. This study measured a PA base concentration of ~ 70 ng/L in stream water adjacent to an invasive PA-producing plant Petasites hybridus (Asteraceae). After intense rain the PA concentration increased tenfold. In addition, PAs measured up to 230 ng/L in seepage water from groundwater wells. The dominant PAs in both water types corresponded to the most abundant PAs in the plants (senkirkine, senecionine, senecionine N-oxide). The study presents the first discovery of persistent plant toxins in well water and their associated risks. In addition, it for the first time reports monocrotaline and monocrotaline N-oxide in Petasites sp.