Impacts of biochar materials on copper speciation, bioavailability, and toxicity in chromated copper arsenate polluted soil.

Trace element polluted soils pose risks to human and environmental health. Biochar can decrease trace element bioavailability in soils, but their resulting ability to reduce soil toxicity may vary significantly depending on feedstocks used, pyrolysis conditions, and the target pollutants. Chromated copper arsenate (CCA) polluted sites are common, but only very few types of biochar have been tested for these sites. Hence, we tested fourteen well-characterized biochar materials for their ability to bind Cu and reduce toxicity in a CCA polluted soil in a 56-day experiment. Biochar (1%, wt/wt) increased plant (wheat, Triticum aestivum L.) shoot and root growth by 6-58% and 0-73%, reduced soil toxicity to Arthrobacter globiformis by 7-55%, decreased bioavailable Cu (Pseudomonas fluorescens bioreporter) by 5-65%, and decreased free Cu2+ ion activities by 27-89%. The A. globiformis solid-contact test constituted a sensitive ecotoxicological endpoint and deserves further attention for assessment of soil quality. Oil seed rape straw biochar generally performed better than other tested biochar materials. Biochar performance was positively correlated with its high cation exchange capacity, multiple surface functional groups, and high nitrogen and phosphorus content. Our results pave the way for future selection of feedstocks for creation of modified biochar materials with optimal performance in CCA polluted soil.

Long-term phosphorus removal by Ca and Fe-rich drainage filter materials under variable flow and inlet concentrations.

Phosphorus (P) losses from tile-drained agricultural fields may degrade surface water quality by accelerating eutrophication. Among the different edge-of-field technologies, compact filter systems using different filter materials have been identified as potentially effective solutions for removing P from drainage water before discharge downstream. This study investigated the long-term (>696 days) P removal efficiency of 5 different filter materials in a column setup, using artificial drainage water (pH 6). Filter materials included two iron-based granulates (calcinated diatomaceous earth (CDE), ferric hydroxide granules (CFH)), and three calcium-based granulates (seashells, limestone, calcinated silicate/calcium oxide (Filtralite-P)). Experiments were performed under variable flow rates (0.037 and 1.52 L h-1; hydraulic retention time of 26-43 min and 18-30 h) and inlet P concentrations (0.14 and 0.7 mg L-1). An overall analysis revealed that the Fe-based materials achieved higher P retention than Ca-based materials. In particular, CFH was capable of retaining 99 and 98 % of the high and low inlet P concentrations, respectively. Conversely, limestone retained only 25 % of the high P load. CDE performed moderately well, independently of the inlet P concentration. Filtralite-P and Seashells performed well at high inlet P concentration but relatively poorly at low P concentration. The sensitivity of filter material P removal efficiency to variations in P loading was generally lowest for CFH and highest for limestone.

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.

Effects of sulfur application on cadmium accumulation in brown rice under wheat-rice rotation.

We investigated how sulfur (S) application prior to wheat cultivation under wheat-rice rotation influences the uptake of cadmium (Cd) in rice grown in low- and high-Cd soils. A pot experiment was conducted with four S levels (0, 30, 60, 120 mg S kg-1) and two Cd rates (low and high, 0.35 and 10.35 mg Cd kg-1) supplied to wheat. Part of the wheat straw was returned to the soil before planting rice, which was cultivated for 132 days. To explore the key mechanisms by which S application controlled Cd accumulation in brown rice, (1) soil pore water at the key growth stages was sampled, and dissolved Cd and S species concentrations were determined; (2) rice plant tissues (including iron plaque on the root surface) were sampled at maturity for Cd and S analysis. With increasing S level, Cd accumulation in brown rice peaked at 60 mg S kg-1, irrespective of soil Cd levels. For high-Cd soils, concentrations of Cd in brown rice increased by 57%, 228%, and 100% at 30, 60, and 120 mg S kg-1, respectively, compared with no S treatment. The increase in brown rice Cd by low S levels (0-60 mg kg-1) could be attributed to (1) the S-induced increase in soil pore water sulfate increasing the Cd influx into rice roots and (2) the S-induced increase in leaf S promoting Cd translocation into brown rice. However, brown rice Cd decreased at 120 mg S kg-1 due to (1) low Cd solubility at 120 mg S kg-1 and (2) root and leaf S uptake, which inhibited Cd uptake. Sulfur application to wheat crop increased the risk of Cd accumulation in brown rice. Thus, applying S-containing fertilizers to Cd-contaminated paddy soils is not recommended.

Adsorption of arsenic(V) onto single sheet iron oxide: X-ray absorption fine structure and surface complexation.

Adsorption onto two-dimensional nanosheet materials offers new possibilities for fast and efficient removal of contaminants from waters. Here, the adsorption of As(V) to a new type of iron oxides - single sheet iron oxide (SSI) - has been studied as a function of time, loading and pH. Adsorption of As(V) onto SSI was very fast compared to other iron oxides, with 80% of total As(V) adsorbed within 10 min. Examination by extended X-ray absorption fine structure analysis showed that As(V) forms a bidentate inner-sphere surface complex with SSI. Arsenic(V) adsorption isotherms and adsorption envelopes were well described using a 1-pK Basic Stern surface complexation model involving protonated (Fe2O2AsO2H-) and unprotonated (Fe2O2AsO2-2) inner-sphere surface complexes. The surface complexation constants for As(V) binding to SSI is similar to constants found for goethite and ferrihydrite. Simulated adsorption isotherms for intermediate As(V) concentrations also demonstrate that SSI is performing equally well as goethite and ferrihydrite based on surface area normalized adsorption capacities. The binding affinities at micromolar to submicromolar As(V) solution concentrations are similar for SSI and ferrihydrite. SSI has interesting potential as a stable, high-affinity sorbent for use in applications where efficient and fast removal is required.

Stability of saponin biopesticides: hydrolysis in aqueous solutions and lake waters.

Saponins form a group of plant-produced glycosides with potential as biopesticide ingredients. The environmental fate of saponins has never been fully investigated. In the present study, we use QS-18, a specific saponin from Quillaja saponaria as an example, to quantify hydrolysis under different conditions of pH, temperature and water chemical composition. Saponin hydrolysis in buffer solutions was base-catalyzed and followed first-order kinetics. Thus, hydrolysis was slow at pH 5.1 with a half-life of 330 ± 220 d (26 °C), which increases to 0.06 ± 0.01 d at pH 10.0. Hydrolysis rates were highly sensitive to temperature with an activation energy of 56.9 ± 14.2 kJ mol-1 at pH 7.2. In strong contrast, hydrolysis in lake waters (pH 6.4-8.2) produced different patterns with a fast initial dissipation of 25 to 60% of the added saponin within the first five hours, followed by an extremely slow reaction with 25 to 75% unreacted saponin left after reaction times longer than 120 h. The fast dissipation followed by slow hydrolysis in lake water was hypothesized to be attributed to sorption and/or flocculation of saponins by inorganic nanoparticles and/or solutes in the lake water followed by inactivation of hydrolysis due to the sorption/flocculation. The present study demonstrates that saponins may hydrolyze slowly under acidic and cold conditions. In addition, it demonstrates that dissipation kinetics in natural waters may deviate substantially from the kinetics predicted based on laboratory experiments with "clean" buffered solutions. This emphasizes the need for a deeper understanding of the processes affecting the dissipation kinetics of potential toxins under natural conditions, as fate models based on laboratory derived kinetic data may be seriously flawed.

What is the aquatic toxicity of saponin-rich plant extracts used as biopesticides?

Saponin-rich extracts from Quillaja saponaria and Chenopodium quinoa have been registered by US EPA as active ingredients in biopesticides, and extract from tea seed powder, Camellia oleifera has been proposed for biocidal use. If saponin-rich biopesticides are efficient against pests, they are most likely also bioactive in the aquatic environment against non-target organisms. The aim of this study was to conduct an effect assessment of saponin-rich plant extracts by using species sensitivity distributions based on acute toxicity tests. The maximal concentrations protecting 95% of the aquatic species (HC5) of saponins extracted from quillaja bark, tea seed coat and quinoa seed coat were 2.91 ±â€¯1.00, 0.22 ±â€¯0.11 and 22.9 ±â€¯5.84 mg/L, respectively. The 100-fold difference in toxicity between the saponin-rich extracts from different plant species, indicate that saponin toxicity depends on the species it origins from, making "read-across" between saponins a dubious exercise. In addition, the predicted environmental concentrations of different saponins are close to or higher than their water quality standard, which means that the extracts might pose a risk to the aquatic environment if not used cautiously.

Where does the toxicity come from in saponin extract?

Saponin-rich plant extracts contain bioactive natural compounds and have many applications, e.g. as biopesticides and biosurfactants. The composition of saponin-rich plant extracts is very diverse, making environmental monitoring difficult. In this study various ecotoxicity data as well as exposure data have been collected to explore which compounds in the plant extract are relevant as plant protection agents and furthermore to clarify which compounds may cause undesired side-effects due to their toxicity. Hence, we quantified the toxicity of different fractions (saponins/non-saponins) in the plant extracts on the aquatic crustacean Daphnia magna and zebrafish (Danio rerio) embryos. In addition, we tested the toxicity changes during saponin degradation as well. The results confirm that saponins are responsible for the majority of toxicity (85.1-93.6%) of Quillaja saponaria extract. We, therefore, suggest saponins to be the main target of saponin-rich plant extracts, for instance in the saponin-based biopesticide regulation. Furthermore, we suggest that an abundant saponin fraction, QS-18 from Q. saponaria, can be a key monitoring target to represent the environmental concentration of the saponins, as it contributes with 26% and 61% of the joint toxicity to D. magna and D. rerio, respectively out of the total saponins. The degradation products of saponins are 3-7 times less toxic than the parent compound; therefore the focus should be mainly on the parent compounds.

Selective removal of heavy metal ions by disulfide linked polymer networks.

Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions-copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water.

Concentrations of and health risks posed by polychlorinated dibenzo-p-dioxins and dibenzofurans around industrial sites in Hebei Province, China.

Sintering and steel production as the main emission sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) may affect environment and human health. The concentrations, profiles, and distributions of PCDD/Fs in soil samples from around four typical sintering and steel production plants in Hebei Province, China, were determined. Forty-six soil samples were collected at distances from 500 to 9000 m from industrial plant chimneys. The concentrations of total 17 2,3,7,8-substituted PCDD/F congeners in the soil samples from sites A, B, C, and D were in the range 11-130, 13-284, 2.6-378, and 21-231 pg/g, respectively, and the internationally accepted toxic equivalent (I-TEQ) concentrations were 0.37-13.2, 0.31-12.1, 0.13-13.7, and 1.60-22.7 pg I-TEQ/g, respectively. Soil ingestion was estimated the major exposure pathway to PCDD/Fs. At current PCDD/F concentrations, the local population will be exposed to low amounts of PCDD/Fs in soil from around the industrial sites, and this exposure will pose potential health risks for the local population living at distances of less than 1000 m from nearest stack but will have no high health risks for people living further away. These results will be helpful when planning measures to control PCDD/F sources. The data will also benefit local environmental monitoring studies and be useful when assessing the risks posed by PCDD/Fs around the industrial sites to the environment and humans.

Influence of long-range atmospheric transportation (LRAT) on mono-to octa-chlorinated PCDD/Fs levels and distributions in soil around Qinghai Lake, China.

Long-range atmospheric transportation (LRAT) of persistent organic pollutants followed by their deposition in cold, arid regions is of wide concern. This problem occurs at Qinghai Lake in the northeastern Tibetan Plateau, a sparsely populated area with extreme weather conditions and little current or historical anthropogenic pollution. The concentrations and distribution patterns of the mono-to octa-chlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) congeners in surface soil samples collected from around Qinghai Lake were quantified. Concentration differences between low-(mono-to tri-) chlorinated PCDD/Fs and high-(tetra-to octa-) chlorinated PCDD/Fs were measured. High PCDD/F levels were detected, with total concentrations of 15,108 ± 6323 pg/g for the 27 PCDD/F congeners and 15,104 ± 6324 pg/g for the low-chlorinated PCDD/Fs. The concentrations of 17 2,3,7,8-substituted PCDD/Fs were only 3.1 ± 4.4 pg/g and the corresponding international toxicity equivalency (I-TEQ) was 0.11 ± 0.22 pg I-TEQ/g. Given their higher vapor pressures and lower boiling points, low-chlorinated PCDD/Fs, were predominantly gaseous, whereas high-chlorinated PCDD/Fs were predominantly solid, indicating that there is a higher potential for long-range transport of low-chlorinated PCDD/Fs. Overall, because of their high LRAT potential, low-chlorinated PCDD/Fs may pose a greater risk to local ecosystems in cold, remote areas than high-chlorinated PCDD/Fs.