Fog controls biological cycling of soil phosphorus in the Coastal Cordillera of the Atacama Desert.

Soils in hyper-arid climates, such as the Chilean Atacama Desert, show indications of past and present forms of life despite extreme water limitations. We hypothesize that fog plays a key role in sustaining life. In particular, we assume that fog water is incorporated into soil nutrient cycles, with the inland limit of fog penetration corresponding to the threshold for biological cycling of soil phosphorus (P). We collected topsoil samples (0-10 cm) from each of 54 subsites, including sites in direct adjacency (<10 cm) and in 1 m distance to plants, along an aridity gradient across the Coastal Cordillera. Satellite-based fog detection revealed that Pacific fog penetrates up to 10 km inland, while inland sites at 10-23 km from the coast rely solely on sporadic rainfall for water supply. To assess biological P cycling we performed sequential P fractionation and determined oxygen isotope of HCl-extractable inorganic P δ 18 O HCl - P i $$ \mathrm{P}\ \left({\updelta}^{18}{\mathrm{O}}_{\mathrm{HCl}-{\mathrm{P}}_{\mathrm{i}}}\right) $$ . Total P (Pt ) concentration exponentially increased from 336 mg kg-1 to a maximum of 1021 mg kg-1 in inland areas ≥10 km. With increasing distance from the coast, soil δ 18 O HCl - P i $$ {\updelta}^{18}{\mathrm{O}}_{\mathrm{HCl}-{\mathrm{P}}_{\mathrm{i}}} $$ values declined exponentially from 16.6‰ to a constant 9.9‰ for locations ≥10 km inland. Biological cycling of HCl-Pi near the coast reached a maximum of 76%-100%, which could only be explained by the fact that fog water predominately drives biological P cycling. In inland regions, with minimal rainfall (<5 mm) as single water source, only 24 ± 14% of HCl-Pi was biologically cycled. We conclude that biological P cycling in the hyper-arid Atacama Desert is not exclusively but mainly mediated by fog, which thus controls apatite dissolution rates and related occurrence and spread of microbial life in this extreme environment.

Plastic Fruit Stickers in Industrial Composting─Surface and Structural Alterations Revealed by Electron Microscopy and Computed Tomography.

Often large quantities of plastics are found in compost, with price look-up stickers being a major but little-explored component in the contamination path. Stickers glued to fruit or vegetable peels usually remain attached to the organic material despite sorting processes in the composting plant. Here, we investigated the effects of industrial composting on the structural alterations of these stickers. Commercial polypropylene (PP) stickers on banana peels were added to a typical organic material mixture for processing in an industrial composting plant and successfully resampled after a prerotting (11 days) and main rotting step (25 days). Afterward, both composted and original stickers were analyzed for surface and structural changes via scanning electron microscopy, Fourier-transform infrared spectroscopy, and micro- and nano-X-ray computed tomography (CT) combined with deep learning approaches. The composting resulted in substantial surface changes and degradation in the form of microbial colonization, deformation, and occurrence of cracks in all stickers. Their pore volumes increased from 16.7% in the original sticker to 26.3% at the end of the compost process. In a similar way, the carbonyl index of the stickers increased. Micro-CT images additionally revealed structural changes in the form of large adhesions that penetrated the surface of the sticker. These changes were accompanied by delamination after 25 days of composting, thus overall hinting at the degradation of the stickers and the subsequent formation of smaller microplastic pieces.

Distinct Assembly Patterns of Soil Antibiotic Resistome Revealed by Land-Use Changes over 30 Years.

Compared with the ever-growing information about the anthropogenic discharge of nutrients, metals, and antibiotics on the disturbance of antibiotic resistance genes (ARGs), less is known about how the potential natural stressors drive the evolutionary processes of antibiotic resistance. This study examined how soil resistomes evolved and differentiated over 30 years in various land use settings with spatiotemporal homogeneity and minimal human impact. We found that the contents of soil organic carbon, nitrogen, soil microbial biomass, and bioavailable heavy metals, as well as related changes in the antibiotic resistome prevalence including diversity and abundance, declined in the order of grassland > cropland > bareland. Sixty-nine remaining ARGs and 14 mobile genetic elements (MGEs) were shared among three land uses. Multiple factors (i.e., soil properties, heavy metals, bacterial community, and MGEs) contributed to the evolutionary changes of the antibiotic resistome, wherein the resistome profile was dominantly driven by MGEs from both direct and indirect pathways, supported by a partial least-squares path model analysis. Our results suggest that pathways to mitigate ARGs in soils can coincide with land degradation processes, posing a challenge to the common goal of managing our environment sustainably.

18O Isotope Labeling Combined with 31P Nuclear Magnetic Resonance Spectroscopy for Accurate Quantification of Hydrolyzable Phosphorus Species in Environmental Samples.

31P nuclear magnetic resonance (NMR) spectra can be biased due to the hydrolysis of labile P species during sample treatment and NMR analysis. This paper offers an approach to circumvent this problem by performing sample preparation and analysis in 18O-enriched medium. Heavy 18O isotope atoms were introduced into the resulting artificial hydrolysis products. The NMR signal of 18O-labeled P was shifted upfield relative to the unlabeled P nuclei in natural metabolites. This isotope shift enabled an immediate differentiation of artificial hydrolysis products from natural metabolites. Moreover, the hydrolysis products could be accurately quantified. Our data suggest that the extent to which artificial hydrolysis alters NMR spectra varies among different types of environmental samples. For instance, 72-84% of the detected monoesters in the organic soils of this study were actually artificially hydrolyzed diesters. By contrast, artificial hydrolysis products in the mineral soils used for this study accounted for less than 6% of the total monoesters. Polyphosphate was also hydrolyzed to yield 18O-labeled products in algal biomass.

Tracing uptake and translocation of phosphorus in wheat using oxygen isotopes and mathematical modelling.

Understanding P uptake in soil-plant systems requires suitable P tracers. The stable oxygen isotope ratio in phosphate (expressed as δ18 OP ) is an alternative to radioactive labelling, but the degree to which plants preserve the δ18 OP value of the P source is unclear. We hypothesised that the source signal will be preserved in roots rather than shoots. In soil and hydroponic experiments with spring wheat (Triticum aestivum), we replaced irrigation water by 18 O-labelled water for up to 10 d. We extracted plant inorganic phosphates with trichloroacetic acid (TCA), assessed temporal dynamics of δ18 OTCA-P values after changing to 18 O-labelled water and combined the results with a mathematical model. Within 1 wk, full equilibration of δ18 OTCA-P values with the isotope value of the water in the growth medium occurred in shoots but not in roots. Model results further indicated that root δ18 OTCA-P values were affected by back transport of phosphate from shoots to roots, with a greater contribution of source P at higher temperatures when back transport was reduced. Root δ18 OTCA-P partially preserved the source signal, providing an indicator of P uptake sources. This now needs to be tested extensively for different species, soil and climate conditions to enable application in future ecosystem studies.

Conservation with elevated elephant densities sequesters carbon in soils despite losses of woody biomass.

Nature conservation and restoration in terrestrial ecosystems is often focused on increasing the numbers of megafauna, expecting them to have positive impacts on ecological self-regulation processes and biodiversity. In sub-Saharan Africa, conservation efforts also aspire to protect and enhance biodiversity with particular focus on elephants. However, elephant browsing carries the risk of woody biomass losses. In this context, little is known about how increasing elephant numbers affects carbon stocks in soils, including the subsoils. We hypothesized that (1) increasing numbers of elephants reduce tree biomass, and thus the amount of C stored therein, resulting (2) in a loss of soil organic carbon (SOC). If true, a negative carbon footprint could limit the sustainability of elephant conservation from a global carbon perspective. To test these hypotheses, we selected plots of low, medium, and high elephant densities in two national parks and adjacent conservancies in the Namibian component of the Kavango Zambezi Transfrontier Area (KAZA), and quantified carbon storage in both woody vegetation and soils (1 m). Analyses were supplemented by the assessment of soil carbon isotopic composition. We found that increasing elephant densities resulted in a loss of tree carbon storage by 6.4 t ha-1 . However, and in contrast to our second hypothesis, SOC stocks increased by 4.7 t ha-1 with increasing elephant densities. These higher SOC stocks were mainly found in the topsoil (0-30 cm) and were largely due to the formation of SOC from woody biomass. A second carbon input source into the soils was megaherbivore dung, which contributed with 0.02-0.323 t C ha-1  year-1 to ecosystem carbon storage in the low and high elephant density plots, respectively. Consequently, increasing elephant density does not necessarily lead to a negative C footprint, as soil carbon sequestration and transient C storage in dung almost compensate for losses in tree biomass.

Apple Replant Disease: Causes and Mitigation Strategies.

After replanting apple (Malus domestica Borkh.) on the same site severe growth suppressions, and a decline in yield and fruit quality are observed in all apple producing areas worldwide. The causes of this complex phenomenon, called apple replant disease (ARD), are only poorly understood up to now which is in part due to inconsistencies in terms and methodologies. Therefore we suggest the following definition for ARD: ARD describes a harmfully disturbed physiological and morphological reaction of apple plants to soils that faced alterations in their (micro-) biome due to the previous apple cultures. The underlying interactions likely have multiple causes that extend beyond common analytical tools in microbial ecology. They are influenced by soil properties, faunal vectors, and trophic cascades, with genotype-specific effects on plant secondary metabolism, particularly phytoalexin biosynthesis. Yet, emerging tools allow to unravel the soil and rhizosphere (micro-) biome, to characterize alterations of habitat quality, and to decipher the plant reactions. Thereby, deep insights into the reactions taking place at the root rhizosphere interface will be gained. Counteractions are suggested, taking into account that culture management should emphasize on improving soil microbial and faunal diversity as well as habitat quality rather than focus on soil disinfection.

Spatial Microanalysis of Natural 13C/12C Abundance in Environmental Samples Using Laser Ablation-Isotope Ratio Mass Spectrometry.

The stable 13C/12C isotope composition usually varies among different organic materials due to isotope fractionation during biochemical synthesis and degradation processes. Here, we introduce a novel laser ablation-isotope ratio mass spectrometry (LA-IRMS) methodology that allows highly resolved spatial analysis of carbon isotope signatures in solid samples down to a spatial resolution of 10 µm. The presented instrumental setup includes in-house-designed exchangeable ablation cells (3.8 and 0.4 mL, respectively) and an improved sample gas transfer, which allow accurate δ13C measurements of an acryl plate standard down to 0.6 and 0.4 ng of ablated carbon, respectively (standard deviation 0.25‰). Initial testing on plant and soil samples confirmed that microheterogeneity of their natural 13C/12C abundance can now be mapped at a spatial resolution down to 10 µm. The respective δ13C values in soils with C3/C4 crop sequence history varied by up to 14‰ across a distance of less than 100 µm in soil aggregates, while being partly sorted along rhizosphere gradients of <300 µm from Miscanthus plant roots into the surrounding soil. These very first demonstrations point to the appearance of very small metabolic hotspots originating from different natural isotope discrimination processes, now traceable via LA-IRMS.

Quantitative assessment of microbial necromass contribution to soil organic matter.

Soil carbon transformation and sequestration have received significant interest in recent years due to a growing need for quantitating its role in mitigating climate change. Even though our understanding of the nature of soil organic matter has recently been substantially revised, fundamental uncertainty remains about the quantitative importance of microbial necromass as part of persistent organic matter. Addressing this uncertainty has been hampered by the absence of quantitative assessments whether microbial matter makes up the majority of the persistent carbon in soil. Direct quantitation of microbial necromass in soil is very challenging because of an overlapping molecular signature with nonmicrobial organic carbon. Here, we use a comprehensive analysis of existing biomarker amino sugar data published between 1996 and 2018, combined with novel appropriation using an ecological systems approach, elemental carbon-nitrogen stoichiometry, and biomarker scaling, to demonstrate a suit of strategies for quantitating the contribution of microbe-derived carbon to the topsoil organic carbon reservoir in global temperate agricultural, grassland, and forest ecosystems. We show that microbial necromass can make up more than half of soil organic carbon. Hence, we suggest that next-generation field management requires promoting microbial biomass formation and necromass preservation to maintain healthy soils, ecosystems, and climate. Our analyses have important implications for improving current climate and carbon models, and helping develop management practices and policies.

Quantitative imaging of 33P in plant materials using 14C polymer references.

Phosphorus (P) research still lacks techniques for rapid imaging of P use and allocation in different soil, sediment, and biological systems in a quantitative manner. In this study, we describe a time-saving and cost-efficient digital autoradiographic method for in situ quantitative imaging of 33P radioisotopes in plant materials. Our method combines autoradiography of the radiotracer applications with additions of commercially available 14C polymer references to obtain 33P activities in a quantitative manner up to 2000 Bq cm-2. Our data show that linear standard regressions for both radioisotopes are obtained, allowing the establishment of photostimulated luminescence equivalence between both radioisotopes with a factor of 9.73. Validating experiments revealed a good agreement between the calculated and applied 33P activity (R2 = 0.96). This finding was also valid for the co-exposure of 14C polymer references and 33P radioisotope specific activities in excised plant leaves for both maize (R2 = 0.99) and wheat (R2 = 0.99). The outlined autoradiographic quantification procedure retrieved 100% ± 12% of the 33P activity in the plant leaves, irrespective of plant tissue density. The simplicity of this methodology opens up new perspectives for fast quantitative imaging of 33P in biological systems and likely, thus, also for other environmental compartments.

Diffusion-Ordered Nuclear Magnetic Resonance Spectroscopy (DOSY-NMR): A Novel Tool for Identification of Phosphorus Compounds in Soil Extracts.

Liquid-state, one-dimension 31P nuclear magnetic resonance spectroscopy (NMR) has greatly advanced our understanding of the composition of organic phosphorus in the environment. However, the correct assignment of signals is complicated by overlapping and shifting signals in different types of soils. We applied therefore for the first time diffusion-ordered spectroscopy (DOSY) to soil extracts, allowing us to separate phosphorus components in the second domain based on their translational diffusion coefficients. After successful application to a mixture of 14 model compounds, diffusion rates correlated closely with the molecular weight of the individual compound in aqueous solution (R2 = 0.97). The method was then applied to NaOH/EDTA extracts of a grassland soil, of which paramagnetic contaminations were removed with sodium sulfide following high-velocity centrifugation (21 500g, 45 min) at 4 °C. Diffusion rates in soil extracts were again closely related to molecular weight (R2 = 0.98), varying from 163.9 to 923.8 Da. However, our DOSY application failed for a forest soil with low organic phosphorus content. Overall, DOSY did help to clearly identify specific NMR signals like myo- and scyllo-inositol hexakisphosphate. It thus provides a more confident signal assignment than 1D 31P NMR, although currently the ubiquitous use of this novel methodology is still limited to soils with high organic phosphorus content.

Tracing copper derived from pig manure in calcareous soils and soil leachates by 65Cu labeling.

Copper is used as a growth promoter in animal husbandry, resulting in high Cu concentrations in animal manure. We tested whether Cu would be mobilized in soils receiving excessive loads of manure, both from recently added and from aged fractions. To discriminate between these Cu sources, manure was labeled with (65)Cu. After soil application of 0, 15, and 30 Mg manure ha(-1), leachate was collected in free-draining lysimeters (40 cm depth) under undisturbed soil over a 53 day period. Determining the total amounts of Cu and the fractions of (65)Cu in leachate and the soil profile enabled us to trace the translocation of Cu derived from labeled manure. More than 84% of the applied Cu was retained in the top 2 cm of soil. Less than 0.01% of the applied Cu was detected overall in the leachate. Of this amount, however, 38% (± 8.9 SE) was leached within 8 days after application. The total Cu concentration in leachates (32-164 µg L(-1)) frequently exceeded the Chinese groundwater quality standard of 50 µg L(-1). The added (65)Cu, however, accounted for less than 3.6% of the total Cu leaching load, suggesting that Cu from older sources and/or geological background controls contamination, regardless of current land management.

Phosphorus Containing Water Dispersible Nanoparticles in Arable Soil.

Due to the limited solubility of phosphorus (P) in soil, understanding its binding in fine colloids is vital to better forecast P dynamics and losses in agricultural systems. We hypothesized that water-dispersible P is present as nanoparticles and that iron (Fe) plays a crucial role for P binding to these nanoparticles. To test this, we isolated water-dispersible fine colloids (WDFC) from an arable topsoil (Haplic Luvisol, Germany) and assessed colloidal P forms after asymmetric flow field-flow fractionation coupled with ultraviolet and an inductively coupled plasma mass spectrometer, with and without removal of amorphous and crystalline Fe oxides using oxalate and dithionite, respectively. We found that fine colloidal P was present in two dominant sizes: (i) in associations of organic matter and amorphous Fe (Al) oxides in nanoparticles <20 nm, and (ii) in aggregates of fine clay, organic matter and Fe oxides (more crystalline Fe oxides) with a mean diameter of 170 to 225 nm. Solution P-nuclear magnetic resonance spectra indicated that the organically bound P predominantly comprised orthophosphate-monoesters. Approximately 65% of P in the WDFC was liberated after the removal of Fe oxides (especially amorphous Fe oxides). The remaining P was bound to larger-sized WDFC particles and Fe bearing phyllosilicate minerals. Intriguingly, the removal of Fe by dithionite resulted in a disaggregation of the nanoparticles, evident in higher portions of organically bound P in the <20 nm nanoparticle fraction, and a widening of size distribution pattern in larger-sized WDFC fraction. We conclude that the crystalline Fe oxides contributed to soil P sequestration by (i) acting as cementing agents contributing to soil fine colloid aggregation, and (ii) binding not only inorganic but also organic P in larger soil WDFC particles.

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.

Soil microbial community responses to antibiotic-contaminated manure under different soil moisture regimes.

Sulfadiazine (SDZ) is an antibiotic frequently administered to livestock, and it alters microbial communities when entering soils with animal manure, but understanding the interactions of these effects to the prevailing climatic regime has eluded researchers. A climatic factor that strongly controls microbial activity is soil moisture. Here, we hypothesized that the effects of SDZ on soil microbial communities will be modulated depending on the soil moisture conditions. To test this hypothesis, we performed a 49-day fully controlled climate chamber pot experiments with soil grown with Dactylis glomerata (L.). Manure-amended pots without or with SDZ contamination were incubated under a dynamic moisture regime (DMR) with repeated drying and rewetting changes of >20 % maximum water holding capacity (WHCmax) in comparison to a control moisture regime (CMR) at an average soil moisture of 38 % WHCmax. We then monitored changes in SDZ concentration as well as in the phenotypic phospholipid fatty acid and genotypic 16S rRNA gene fragment patterns of the microbial community after 7, 20, 27, 34, and 49 days of incubation. The results showed that strongly changing water supply made SDZ accessible to mild extraction in the short term. As a result, and despite rather small SDZ effects on community structures, the PLFA-derived microbial biomass was suppressed in the SDZ-contaminated DMR soils relative to the CMR ones, indicating that dynamic moisture changes accelerate the susceptibility of the soil microbial community to antibiotics.

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.

Identification of soil contamination hotspots with veterinary antibiotics using heavy metal concentrations and leaching data--a field study in China.

In regions with high livestock densities, the usage of antibiotics and metals for veterinary purposes or as growth promoters poses a risk in manured soils. We investigated to which degree the concentrations and depth distributions of Cu, Zn, Cr and As could be used as a tracer to discover contaminations with sulfonamides, tetracyclines and fluoroquinolones. Besides, we estimated the potential vertical translocation of antibiotics and compared the results to measured data. In the peri-urban region of Beijing, China, soil was sampled from agricultural fields and a dry riverbed contaminated by organic waste disposal. The antibiotic concentrations reached 110 µg kg(-1) sulfamethazine, 111 µg kg(-1) chlortetracycline and 62 µg kg(-1) enrofloxacin in the topsoil of agricultural fields. Intriguingly, total concentrations of Cu, Zn, Cr and As were smaller than 65, 130, 36 and 10 mg kg(-1) in surface soil, respectively, therewith fulfilling Chinese quality standards. Correlations between sulfamethazine concentrations and Cu or Zn suggest that in regions with high manure applications, one might use the frequently existing monitoring data for metals to identify potential pollution hotspots for antibiotics in topsoils. In the subsoils, we found sulfamethazine down to ≥2 m depth on agricultural sites and down to ≥4 m depth in the riverbed. As no translocation of metals was observed, subsoil antibiotic contamination could not be predicted from metal data. Nevertheless, sulfonamide stocks in the subsoil could be estimated with an accuracy of 35-200 % from fertilisation data and potential leaching rates. While this may not be sufficient for precise prediction of antibiotic exposure, it may very well be useful for the pre-identification of risk hotspots for subsequent in-depth assessment studies.

Non-extractable residues of perfluorooctanoic acid (PFOA) in soil.

PER: and polyfluoroalkyl substances have gained increased attention due to their persistence, ubiquitous presence in the environment, and toxicity. We hypothesised that the formation of non-extractable residues [NER] occurs in soils and contributes to the overall persistence of these priority pollutants, and that NER formation is controlled by temperature. To test these hypotheses, we used 14C-labelled perfluorooctanoic acid [PFOA] as target compound, added it to two arable soils (Cambisol, Luvisol), and incubated them at 10°C and 20°C in the dark. To support potential co-metabolic decomposition, some samples were additionally fed with glucose to enhance microbial activity. The PFOA residues were then sequentially extracted using 0.01 M CaCl2, followed by accelerated solvent extraction (ASE) with methanol or methanol/acetic acid after 0, 1, 3, 9, 30, 62, and 90 days of incubation. In addition, we monitored the release of 14C into the gas phase as well as [14C]-PFOA-NER after dry combustion and liquid scintillation counting. After 90 days, we found that the [14C]-PFOA content declined in the extraction order of CaCl2 ((bio)available fraction) > ASE (residual fraction) > NER > gas fraction), with most rapid changes occurring in the first 9 days of incubation. NER formation was different in the two soils and reached 5-9% of the applied amount in the Cambisol and Luvisol, respectively. Noteworthy the proportion of 14C-PFOA in the (bio)available fraction remained relatively stable over time at 56-62% of the applied amount, indicating the reversible transfer into this fraction from a bi-exponentially declining residual (ASE) pool. These dissipation patterns were neither influenced by temperature nor by the addition of glucose. We conclude that NER exist for PFOA, but that the majority of PFOA remains in (bio)available form, thus maintaining toxicity and mobility in soil for prolonged periods of time.

Do nanoparticles and colloids replenish soil phosphorus in the rhizosphere of winter wheat?

The rhizosphere is generally depleted in nutrients, but as a hotspot of microbial activity it fosters crop P uptake. We hypothesized that P contents of water extractable nanoparticles (<0.1 µm) and small sized colloids (<0.45 µm) differ between non-rhizosphere and rhizosphere soil. To test this hypothesis, rhizosphere and non-rhizosphere soils (Luvisol and Cambisol) were sampled at harvest period of winter wheat near Selhausen (Germany). Microaggregate and colloidal fractions in the size range of 53-250 µm, 20-53 µm, 0.45-20 µm, and <0.45 µm were separated by wet-sieving and centrifugation. Subsequently, the colloids <0.45 µm were further isolated in 0.66-20 nm, 20-100 nm and 100-450 nm fractions using asymmetric flow field flow fractionation (AF4) and directly analyzed by online coupled organic carbon detector (OCD) and inductively coupled plasma mass spectrometry (ICP-MS) for element composition. No significant differences (p > 0.05) were measured between rhizosphere and non-rhizosphere soil P contents of microaggregate fractions. The rhizosphere soil, however, showed ∼26 % depletion of average P content in the 0.66-20 nm fraction, which went along with an enrichment of P content of the 100-450 nm fraction by a factor of two. Apparently, P uptake by plants results in a redistribution of P in the rhizosphere, with small nanoparticles providing available P to plants while excess residual P is bound to fine colloids.

Dose-dependent reactions of Aporrectodea caliginosa to perfluorooctanoic acid and perfluorooctanesulfonic acid in soil.

As a consequence of their widespread use, e.g. as protective coatings for fabrics, and their resistance to thermal and biological breakdown, perfluorinated compounds are increasingly found in the environment, but little is known about their ecotoxicological properties. A 40-day microcosm experiment was carried out to examine the effects of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) on the endogeic geophagus earthworm Aporrectodea caliginosa, its survival and feeding on soil organic C and microbial biomass C. Three levels of concentration (1, 100, and 500 mg kg(-1)) were chosen. The lowest represented the maximum found in sediments and soils and the other two are extreme concentrations that might occur in pollution hotspots and that have been shown to poison organisms. Earthworms promoted the production of CO2 and decreased microbial biomass C in soil, regardless of the presence of PFOA or PFOS. Both compounds significantly decreased the surviving numbers and dry weight of earthworms at concentrations of 100 mg kg(-1). No earthworms survived at PFOA and PFOS concentrations of 500 mg kg(-1). At concentrations of 1 mg kg(-1), no negative effects were observed. The δ(13)C values of A. caliginosa did not differ between treatments. In contrast, the δ(15)N values were significantly increased after adding 1 mg kg(-1) of PFOA, reflecting elevated portions of soil-derived N in the earthworm tissue. In contrast, these portions of soil-derived N were lower in the earthworms after addition of 100 mg kg(-1) of PFOA and PFOS. In conclusion, extreme concentrations of PFOA and PFOS negatively affected endogeic A. caliginosa, whereas a concentration of 1 mg kg(-1) of PFOA and PFOS was related to an increased uptake of soil N by the earthworms.