Antibiotics reach agricultural soils via fertilization with manure and biosolids as well as irrigation withwastewater and have the potential to be taken up by growing crops. The fate of antibiotics ...in terms of uptakefrom soil to plants, as well as translocation from root to leaves, is determined by a combination of antibiotic'sphysio-chemical (e.g. speciation, lipophilicity), soil (e.g. organic carbon content, pH) and plant (e.g.transpiration rates) characteristics. In this meta-analysis, a literature search was executed to obtain an overview of antibiotic uptake to plants, with an aim to identify uptake and translocation patterns of different antibiotic classes. Overall, we found that higher uptake of tetracyclines to plant leaves was observed compared to sulfonamides. Differences were also observed in translocation within the plants, where tetracyclines were found in roots and leaves with close to equal concentrations, while the sulfonamides represented a tendency to accumulate to the root fraction. The antibiotic's characteristics have a high influence on their fate, for example, the high water-solubility and uncharged speciation in typical agricultural soil pH ranges likely induces tetracycline uptake from soil and translocation in plant. Despite the advances in knowledge over the past decade, our meta-analysis indicated that the available research is focused on a limited number of analytes and antibiotic classes. Furthermore, fastgrowing plant species (e.g. spinach, lettuce, and radish) are overly represented in studies compared to crop species with higher significance for human food sources (e.g. corn, wheat, and potato), requiring more attention in future research.
Biochar and activated carbon, both carbonaceous pyrogenic materials, are important products for environmental technology and intensively studied for a multitude of purposes. A strict distinction ...between these materials is not always possible, and also a generally accepted terminology is lacking. However, research on both materials is increasingly overlapping: sorption and remediation are the domain of activated carbon, which nowadays is also addressed by studies on biochar. Thus, awareness of both fields of research and knowledge about the distinction of biochar and activated carbon is necessary for designing novel research on pyrogenic carbonaceous materials. Here, we describe the dividing ranges and common grounds of biochar, activated carbon and other pyrogenic carbonaceous materials such as charcoal based on their history, definition and production technologies. This review also summarizes thermochemical conversions and non-thermal pre- and post-treatments that are used to produce biochar and activated carbon. Our overview shows that biochar research should take advantage of the numerous techniques of activation and modification to tailor biochars for their intended applications.
Polycyclic aromatic hydrocarbons (PAH) were analysed in 23 soil samples (0–10 cm layer) from the Swiss soil monitoring network (NABO) together with total organic carbon (TOC) and black carbon (BC) ...concentration, as well as some PAH source diagnostic ratios and molecular markers. The concentrations of the sum of 16 EPA priority PAHs ranged from 50 to 619 μg/kg dw. Concentrations increased from arable, permanent and pasture grassland, forest, to urban soils and were 21–89% lower than median numbers reported in the literature for similar Swiss and European soils. NABO soils contained BC in concentrations from 0.4 to 1.8 mg/g dw, except for two sites with markedly higher levels. These numbers corresponded to 1–6% of TOC and were comparable to the limited published BC data in soil and sediments obtained with comparable analytical methods. The various PAH ratios and molecular markers pointed to a domination of pyrogenically formed PAHs in Swiss soils. In concert, the gathered data suggest the following major findings: (1) gas phase PAHs (naphthalene to fluorene) were long-range transported, cold-condensated at higher altitudes, and approaching equilibrium with soil organic matter (OM); (2) (partially) particle-bound PAHs (phenanthrene to benzo
ghiperylene) were mostly deposited regionally in urban areas, and not equilibrated with soil OM; (3) Diesel combustion appeared to be a major emission source of PAH and BC in urban areas; and (4) wood combustion might have contributed significantly to PAH burdens in some soils of remote/alpine (forest) sites.
Due to growing production, carbon nanotubes (CNT) may soon be found in a broad range of products and thus in the environment. In this work, an algal growth test was developed to determine effects of ...pristine and oxidized CNT on the green algae Chlorella vulgaris and Pseudokirchneriella subcapitata. CNT suspensions were prepared in algal test medium and characterized taking into account the suspension age, the reduced light transmittance of nanoparticle suspensions defined as shading of CNT and quantified by UV/vis spectroscopy, and the agglomeration of the CNT and of the algal cells. Growth inhibition and photosynthetic activity were investigated as end points. Growth of C. vulgaris was inhibited with effect concentrations of 50% (EC50) values of 1.8 mg CNT/L and of 24 mg CNT/L in well dispersed and in agglomerated suspensions, respectively, and 20 mg CNT/L and 36 mg CNT/L for P. subcapitata, respectively. However, the photosynthetic activity was not affected. Growth inhibition was highly correlated with the shading of CNT and the agglomeration of algal cells. This suggests that the reduced algal growth might be caused mainly by indirect effects, i.e. by reduced availability of light and different growth conditions caused by the locally elevated algal concentration inside of CNT agglomerates.
Biochar is increasingly promoted as a beneficial soil conditioner. However, it may contain residues of polycyclic aromatic hydrocarbons (PAHs) as a result of its production by pyrolysis. To date, ...analytical methods to analyze PAHs in biochar quantitatively are hardly available. This study presents an optimized and validated procedure to quantify the 16 U.S. EPA PAHs in biochar. PAHs were best extracted with Soxhlet for 36 h using 100% toluene. Average absolute recoveries of isotope labeled internal standards used for each analyte from three different biochars ranged from 42% to 72%, and relative recoveries were between 71% and 105%. The limits of detection were biochar-dependent, but on average a factor of >50 lower than quantified PAH concentrations (9–355 mg kgdry weight –1). The established method prepares the ground for a harmonized protocol for PAH analysis of biochars, a necessity for biochar quality control, registration, and legislation.
Pyrogenic carbon (PyC), produced naturally (wildfire charcoal) and anthropogenically (biochar), is extensively studied due to its importance in several disciplines, including global climate dynamics, ...agronomy and paleosciences. Charcoal and biochar are commonly used as analogues for each other to infer respective carbon sequestration potentials, production conditions, and environmental roles and fates. The direct comparability of corresponding natural and anthropogenic PyC, however, has never been tested. Here we compared key physicochemical properties (elemental composition, δ
C and PAHs signatures, chemical recalcitrance, density and porosity) and carbon sequestration potentials of PyC materials formed from two identical feedstocks (pine forest floor and wood) under wildfire charring- and slow-pyrolysis conditions. Wildfire charcoals were formed under higher maximum temperatures and oxygen availabilities, but much shorter heating durations than slow-pyrolysis biochars, resulting in differing physicochemical properties. These differences are particularly relevant regarding their respective roles as carbon sinks, as even the wildfire charcoals formed at the highest temperatures had lower carbon sequestration potentials than most slow-pyrolysis biochars. Our results challenge the common notion that natural charcoal and biochar are well suited as proxies for each other, and suggest that biochar's environmental residence time may be underestimated when based on natural charcoal as a proxy, and vice versa.
A multi-residue trace analytical method is presented to accurately quantify 146 currently used pesticides in (agricultural) soils with varying soil properties. Pesticides were extracted using an ...optimized quick, easy, cheap, effective, rugged, and safe (QuEChERS) approach and chemical analysis was carried out by liquid chromatography coupled to tandem mass spectrometry (triple quadrupole). Quantification was based on matrix-matched internal standards calibration, using 95 isotopically labeled analyte analogues. In contrast to the common approach of method validation using soils freshly spiked with analytes shortly before the extraction, our method is additionally validated via an in-house prepared partly aged soil, which contains all target pesticides and via agricultural field soils with native pesticide residues. The developed method is highly sensitive (median method limit of quantification: 0.2 ng/g), precise (e.g., median intra-day and inter-day method precision both ~ 4% based on field soils), and true ((i) quantified pesticide concentrations of the partly aged soil remained stable during 6 months, were close to the initially spiked nominal concentration of 10 ng/g, and thus can be used to review trueness in the future; (ii) median freshly spiked relative recovery: 103%; and (iii) participation in a ring trial: median
z
-scores close to one (good to satisfactory result)). Its application to selected Swiss (agricultural) soils revealed the presence of in total 77 different pesticides with sum concentrations up to 500 ng/g. The method is now in use for routine soil monitoring as part of the
Swiss Action Plan for Risk Reduction and Sustainable Use of Plant Protection Products
.
Graphical abstract
The production of toxic plant secondary metabolites (phytotoxins) for defense is a widespread phenomenon in the plant kingdom and is even present in agricultural crops. These phytotoxins may have ...similar characteristics to anthropogenic micropollutants in terms of persistence and toxicity. However, they are only rarely included in environmental risk assessments, partly because a systematic overview of phytotoxins is missing. Here, we present a newly developed, freely available database, Toxic Plants–PhytoToxins (TPPT), containing 1586 phytotoxins of potential ecotoxicological relevance in Central Europe linked to 844 plant species. Our database summarizes phytotoxin patterns in plant species and provides detailed biological and chemical information as well as in silico estimated properties. Using the database, we evaluated phytotoxins regarding occurrence, approximated from the frequencies of Swiss plant species; environmental behavior based on aquatic persistence and mobility; and toxicity. The assessment showed that over 34% of all phytotoxins are potential aquatic micropollutants and should be included in environmental investigations.
Pyrogenic carbonaceous materials (PCM) are increasingly used in a wide variety of consumer products, ranging from medicine, personal care products, food and feed additives, as well as drinking water ...purification. Depending on the product category and corresponding legislation, several terms are commonly used for PCM, such as Carbo activatus, C. medicinalis, vegetable carbon (E153), (activated) charcoal, (activated) biochar, or activated carbon. All PCM contain polycyclic aromatic hydrocarbons (PAHs) co-produced during pyrolysis. However, the actual PAH-content of PCM may range from negligibly low to alarmingly high depending on pyrolysis conditions and, if any, subsequent activation. Because of their health risk, PAHs need to be determined in many such PCM containing products, and concentrations are regulated by respective legally binding documents. Several such documents even specify the analytical method to be used. In this paper, we first argue that based on existing literature, currently legally binding methods to quantify PAHs in such products might not be fit for purpose. Secondly, we exemplarily determined PAH concentrations with a method previously optimized for biochar in a selection of 15 PCM or PCM-containing commercial products, illustrating that concentrations up to 30 mg kg−1 can be found. Consumer safety is of concern according to Swiss norms for drinking water and EU regulations for food additives for some of the investigated samples. In fact, some products would not have been allowed to be put on the market, if regulations with fit for purpose analytical methods existed. As PAHs were detected in considerable concentrations when extracted with toluene for 36 h, the authors suggest a corresponding adaption of existing methods and harmonization of the legislation.
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•Many consumer products contain or consist of pyrogenic carbonaceous materials (PCM).•PCM can contain polycyclic aromatic hydrocarbons (PAHs).•Regulated analytical methods for PAHs in PCM are not fit for purpose.•Considerable PAHs concentrations were found in properly analysed consumer products.•Laws concerning PAHs in PCM of consumer products should be adapted and harmonized.
Black carbon (BC) and total organic carbon (TOC) were quantified in the surface soils of Switzerland (N=105) and Delhi (N=36), India, to examine their relationships with contents of polycyclic ...aromatic hydrocarbons (PAH). BC content in Swiss (background) soils (N=104) varied from 0.41 to 4.75mg/g (median: 1.13mg/g) and constituted 1–9% (median: 3%) of TOC. Indian (urban) soils had similar BC concentrations (0.37–2.05mg/g, median: 1.19mg/g), with relatively higher BC/TOC (6–23%, median: 13%). Similar to TOC, BC showed significant positive correlation with lighter PAH, but no correlation with heavier PAH in Swiss soils. In contrast, heavier PAH were significantly correlated only with BC in Delhi soils. It seems that TOC governs the distribution of PAH in organic matter rich background soils, while the proximity to emission sources is reflected by BC–PAH association in urban soils.
Light PAH correlated with TOC in background soils, whereas heavy PAH were associated with BC close to emission sources.
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