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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.

Compost application is a widely recommended agricultural practice to improve soil fertility. As almost all compost is likely polluted with plastic we hypothesize that compost application is a major input pathway for microplastics (MPs) into agricultural soil. To attribute the plastic load of soil to compost application, we investigated MPs in topsoil (0-30 cm) of a controlled, long-term fertilizer trial with application of compost made of municipal biowaste (0, 5, 10, and 20 t ha -1 a -1 ), which ended 11 years ago. Microplastics were analyzed via density separation (ZnCl 2 ) and light microscopy; testing this method recovered 92 ± 10 % of spiked plastic items. The fields of the long-term compost trial showed a MP load of 0-64 items kg -1 , corresponding to MP stocks in the plough layer (0-30 cm) that ranged from 38.2 ± 55.5 million to 171.4 ± 57.5 million items ha -1 . Microplastic stocks and contents increased with increasing amount of compost application. Thus, we confirm compost as a major input pathway for MPs into agricultural soil, with the effect still visible after 11 years. Comparison of calculated plastic input based on MP contents of recent German compost with MP loads found in soil revealed that overall compost application explained <6 % of total MP stocks. We assume that compost applied in earlier days contained higher plastic loads than recent ones, reflecting current awareness and successful efforts in reducing plastic loads during compost production. However, as the plots at the border of the field had up to 18 times higher MP loads than the inner plots of the trial, we suggest that littering also contributed significantly to MP pollution. Thus, even if given compost applications still add plastics to environment, other sources such as littering can already have become the dominating input pathway., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

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., (© 2021 The Authors. Global Change Biology published by John Wiley & Sons Ltd.)

Bioturbation involves the incorporation of residues from the surface soil into the subsoil; however, common small soil 'bioengineers', such as earthworms or termites, are unlikely to transport human artifacts to deeper soil horizons. However, such artifacts occur in the deeper soil horizons within Amazonian Anthrosols (Terra Preta). Here we test the assumption that such tasks could be carried out by fly larvae, which could thus play a crucial role in waste decomposition and associated soil mixing under tropical conditions. We performed two greenhouse experiments with sandy substrate covered with layers of organic waste, ceramic fragments, and black soldier fly larvae (BSFL) (Hermetia illucens (L.) (Dipt.: Stratiomyidae)). We used in-situ images to assess the rate of bioturbation by BSFL, and then designed our main study to observe waste dissipation (reduction of organic carbon and phosphorus contents from waste model trials with and without charcoal) as related to larval-induced changes in soil properties. We found that the bioturbation of macroinvertebrates like BSFL was able to bury even large (> 5 cm) ceramic fragments within hours, which coincided with high soil growth rates (0.5 cm h-1). The sandy soil was subsequently heavily enriched with organic matter and phosphorus originating from organic waste. We conclude that BSFL, and possibly other fly species, are important, previously overlooked soil 'bioengineers', which may even contribute to the burial of artifacts in Anthrosols and other terrestrial waste dumps., Competing Interests: The authors have declared that no competing interests exist.

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., (© 2019 John Wiley & Sons Ltd.)

Liquid-state, one-dimension 31 P 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 (R 2 = 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 (R 2 = 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 31 P NMR, although currently the ubiquitous use of this novel methodology is still limited to soils with high organic phosphorus content.

In January 2011, fuel quality in inland water vessels was changed by EU regulation 2009/30/EC, aiming at improving air quality along waterways. We hypothesized that the implementation of this regulation both lowered the total deposition of polycyclic aromatic hydrocarbons (PAHs) and changed their composition in river valleys. We analyzed parent-, alkylated- and thio-PAHs in soil and vine leaves, at two waterways (Rhine and Moselle, Germany), as well as in one ship-free reference area (Ahr, Germany). Samples were taken annually (2010-2013) in transects perpendicular to the rivers. We did not find any relation of PAH concentration and composition on vine leaves to inland navigation, likely because atmospheric exchange processes distorted ship-specific accumulation patterns. We did find, however, an accumulation of ship-borne PAHs in topsoil near the waterways (1543±788 and 581±252ngg -1 at Moselle and Rhine, respectively), leading to larger PAH concentrations at the Moselle Valley than at the reference area (535±404ngg -1 ) prior to EU fuel regulation. After fuel regulation, the PAH concentrations decreased in topsoils of the Moselle and Rhine Valley by 35±9 and 62±28%, respectively. These changes were accompanied by increasing proportions of dibenzothiophene (DBT) and low molecular weight PAHs. Both, changes in PAH concentrations and composition were traceable within 200 and 350m distance to the river front of Moselle and Rhine, respectively, and likely favored by erosion of topsoil in vineyards. We conclude that the EU regulation was effective in improving soil and thus also air quality within only three years. The impact was greater and spatially more relevant at the Rhine, which may be attributed to the larger traffic volume of inland navigation., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Steroids are used as faecal markers in environmental and in archaeological studies, because they provide insights into ancient agricultural practices and the former presence of animals. Up to now, steroid analyses could only identify and distinguish between herbivore, pig, and human faecal matter and their residues in soils and sediments. We hypothesized that a finer differentiation between faeces of different livestock animals could be achieved when the analyses of several steroids is combined (Δ5-sterols, 5α-stanols, 5β-stanols, epi-5β-stanols, stanones, and bile acids). We therefore reviewed the existing literature on various faecal steroids from livestock and humans and analysed faeces from old livestock breed (cattle, horse, donkey, sheep, goat, goose, and pig) and humans. Additionally, we performed steroid analyses on soil material of four different archaeological periods (sites located in the Lower Rhine Basin, Western Germany, dating to the Linearbandkeramik, Urnfield Period / Bronze Age, Iron Age, Roman Age) with known or supposed faecal inputs. By means of already established and newly applied steroid ratios of the analysed faeces together with results from the literature, all considered livestock faeces, except sheep and cattle, could be distinguished on the basis of their steroid signatures. Most remarkably was the identification of horse faeces (via the ratio: epi-5β-stigmastanol: 5β-stigmastanol + epicoprostanol: coprostanol; together with the presence of chenodeoxycholic acid) and a successful differentiation between goat (with chenodeoxycholic acid) and sheep/cattle faeces (without chenodeoxycholic acid). The steroid analysis of archaeological soil material confirmed the supposed faecal inputs, even if these inputs had occurred several thousand years ago., Competing Interests: The authors have declared that no competing interests exist.

The impact of termites on nutrient cycling and tropical soil formation depends on their feeding habits and related material transformation. The identification of food sources, however, is difficult, because they are variable and changed by termite activity and nest construction. Here, we related the sources and alteration of organic matter in nests from seven different termite genera and feeding habits in the Terra Firme rainforests to the properties of potential food sources soil, wood, and microepiphytes. Chemical analyses comprised isotopic composition of C and N, cellulosic (CPS), non-cellulosic (NCPS), and N-containing saccharides, and molecular composition screening using pyrolysis-field ionization mass spectrometry (Py-FIMS). The isotopic analysis revealed higher soil δ13C (-27.4‰) and δ15N (6.6‰) values in nests of wood feeding Nasutitermes and Cornitermes than in wood samples (δ13C = -29.1‰, δ15N = 3.4‰), reflecting stable-isotope enrichment with organic matter alterations during or after nest construction. This result was confirmed by elevated NCPS:CPS ratios, indicating a preferential cellulose decomposition in the nests. High portions of muramic acid (MurAc) pointed to the participation of bacteria in the transformation processes. Non-metric multidimensional scaling (MDS) revealed increasing geophagy in the sequence Termes < Embiratermes < Anoplotermes and increasing xylophagy for Cornitermes < Nasutitermes., and that the nest material of Constrictotermes was similar to the microepiphytes sample, confirming the report that Constrictotermes belongs to the microepiphyte-feeders. We therewith document that nest chemistry of rainforest termites shows variations and evidence of modification by microbial processes, but nevertheless it primarily reflects the trophic niches of the constructors.

Neolithic and Bronze Age topsoil relicts revealed enhanced extractable phosphorus (P) and plant available inorganic P fractions, thus raising the question whether there was targeted soil amelioration in prehistoric times. This study aimed (i) at assessing the overall nutrient status and the soil organic matter content of these arable topsoil relicts, and (ii) at tracing ancient soil fertilizing practices by respective stable isotope and biomarker analyses. Prehistoric arable topsoils were preserved in archaeological pit fillings, whereas adjacent subsoils served as controls. One Early Weichselian humic zone represented the soil status before the introduction of agriculture. Recent topsoils served as an additional reference. The applied multi-proxy approach comprised total P and micronutrient contents, stable N isotope ratios, amino acid, steroid, and black carbon analyses as well as soil color measurements. Total contents of P and selected micronutrients (I, Cu, Mn, Mo, Se, Zn) of the arable soil relicts were above the limits for which nutrient deficiencies could be assumed. All pit fillings exhibited elevated δ15N values close to those of recent topsoils (δ15N>6 to 7‰), giving first hints for prehistoric organic N-input. Ancient legume cultivation as a potential source for N input could not be verified by means of amino acid analysis. In contrast, bile acids as markers for faecal input exhibited larger concentrations in the pit fillings compared with the reference and control soils indicating faeces (i.e. manure) input to Neolithic arable topsoils. Also black carbon contents were elevated, amounting up to 38% of soil organic carbon, therewith explaining the dark soil color in the pit fillings and pointing to inputs of burned biomass. The combination of different geochemical analyses revealed a sufficient nutrient status of prehistoric arable soils, as well as signs of amelioration (inputs of organic material like charcoal and faeces-containing manure).

Biochar-amended soil has been proven to possess superior sorption capacities for several environmental pollutants compared with pure soil. However, the role of biochar in the immobilization of polar pesticides and their metabolites has hardly been tested. The aim of this study was therefore to investigate the effect of a soil amendment with biochar on the sorption of selected polar herbicides and herbicide metabolites (log Kow 0.3-<2). To simulate worst-case sorption, a sandy soil (1.7% organic matter) was amended with 1.5% biochar (fresh or composted) to determine sorption/desorption isotherms of the test compounds. One herbicide (imazamox) and three herbicide metabolites (methyl-desphenyl-chloridazon, metazachlor oxalic acid, metazachlor sulfonic acid) were tested, i.e. three anionic and one neutral polar compound. The results showed that the presence of biochar increased the sorption capacity of the soil only in the case of the uncharged compound methyl-desphenyl-chloridazon, for which the average distribution coefficients in biochar-amended soils were higher than in pure soil by a factor of 2.1-2.5. However, this effect rather seemed to reflect the increased soil organic carbon content after the addition of biochar than a preferred sorption of methyl-desphenyl-chloridazon to biochar. In the case of the three anionic compounds imazamox, metazachlor oxalic acid and metazachlor sulfonic acid, biochar amendment did not increase the sorption capacity of the soil for these compounds, presumably as a result of its negative net charge. Similarly, desorption experiments did not show any significant effect of the biochar amendment on desorption. This suggests that the potential of using biochar to mitigate the leaching of the tested polar pesticides or metabolites is limited., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

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.

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.

More than 50% of the world's population feeds on rice. Soils used for rice production are mostly managed under submerged conditions (paddy soils). This management, which favors carbon sequestration, potentially decouples surface from subsurface carbon cycling. The objective of this study was to elucidate the long-term rates of carbon accrual in surface and subsurface soil horizons relative to those of soils under nonpaddy management. We assessed changes in total soil organic as well as of inorganic carbon stocks along a 2000-year chronosequence of soils under paddy and adjacent nonpaddy management in the Yangtze delta, China. The initial organic carbon accumulation phase lasts much longer and is more intensive than previously assumed, e.g., by the Intergovernmental Panel on Climate Change (IPCC). Paddy topsoils accumulated 170-178 kg organic carbon ha(-1) a(-1) in the first 300 years; subsoils lost 29-84 kg organic carbon ha(-1) a(-1) during this period of time. Subsoil carbon losses were largest during the first 50 years after land embankment and again large beyond 700 years of cultivation, due to inorganic carbonate weathering and the lack of organic carbon replenishment. Carbon losses in subsoils may therefore offset soil carbon gains or losses in the surface soils. We strongly recommend including subsoils into global carbon accounting schemes, particularly for paddy fields., (© 2012 Blackwell Publishing Ltd.)

Biochar applications to soils can improve soil fertility by increasing the soil's cation exchange capacity (CEC) and nutrient retention. Because biochar amendment may occur with the applications of organic fertilizers, we tested to which extent composting with farmyard manure increases CEC and nutrient content of charcoal and gasification coke. Both types of biochar absorbed leachate generated during the composting process. As a result, the moisture content of gasification coke increased from 0.02 to 0.94 g g, and that of charcoal increased from 0.03 to 0.52 g g. With the leachate, the chars absorbed organic matter and nutrients, increasing contents of water-extractable organic carbon (gasification coke: from 0.09 to 7.00 g kg; charcoal: from 0.03 to 3.52 g kg), total soluble nitrogen (gasification coke: from not detected to 705.5 mg kg; charcoal: from 3.2 to 377.2 mg kg), plant-available phosphorus (gasification coke: from 351 to 635 mg kg; charcoal: from 44 to 190 mg kg), and plant-available potassium (gasification coke: from 6.0 to 15.3 g kg; charcoal: from 0.6 to 8.5 g kg). The potential CEC increased from 22.4 to 88.6 mmol kg for the gasification coke and from 20.8 to 39.0 mmol kg for the charcoal. There were little if any changes in the contents and patterns of benzene polycarboxylic acids of the biochars, suggesting that degradation of black carbon during the composting process was negligible. The surface area of the biochars declined during the composting process due to the clogging of micropores by sorbed compost-derived materials. Interactions with composting substrate thus enhance the nutrient loads but alter the surface properties of biochars., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

The environmental risks caused by the use of fluoroquinolone antibiotics in human therapeutics and animal husbandry are associated with their persistence and (bio)accessibility in soil. To assess these aspects, we administered difloxacin to pigs and applied the contaminated manure to soil. We then evaluated the dissipation and sequestration of difloxacin in soil in the absence and presence of plants within a laboratory trial, a mesocosm trial, and a field trial. A sequential extraction yielded antibiotic fractions of differing binding strength. We also assessed the antibiotic's effects on nitrogen turnover in soil (potential nitrification and denitrification). Difloxacin was hardly (bio)accessible and was very persistent under all conditions studied (dissipation half-life in bulk soil, >217 d), rapidly forming nonextractable residues. Although varying environmental conditions did not affect persistence, dissipation was accelerated in soil surrounding plant roots. Effects on nitrogen turnover were limited due to the compound's strong binding and small (bio)accessibility despite its persistence., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

Irrigation with wastewater releases pharmaceuticals, pathogenic bacteria, and resistance genes, but little is known about the accumulation of these contaminants in the environment when wastewater is applied for decades. We sampled a chronosequence of soils that were variously irrigated with wastewater from zero up to 100 years in the Mezquital Valley, Mexico, and investigated the accumulation of ciprofloxacin, enrofloxacin, sulfamethoxazole, trimethoprim, clarithromycin, carbamazepine, bezafibrate, naproxen, diclofenac, as well as the occurrence of Enterococcus spp., and sul and qnr resistance genes. Total concentrations of ciprofloxacin, sulfamethoxazole, and carbamazepine increased with irrigation duration reaching 95% of their upper limit of 1.4 µg/kg (ciprofloxacin), 4.3 µg/kg (sulfamethoxazole), and 5.4 µg/kg (carbamazepine) in soils irrigated for 19-28 years. Accumulation was soil-type-specific, with largest accumulation rates in Leptosols and no time-trend in Vertisols. Acidic pharmaceuticals (diclofenac, naproxen, bezafibrate) were not retained and thus did not accumulate in soils. We did not detect qnrA genes, but qnrS and qnrB genes were found in two of the irrigated soils. Relative concentrations of sul1 genes in irrigated soils were two orders of magnitude larger (3.15 × 10(-3) ± 0.22 × 10(-3) copies/16S rDNA) than in non-irrigated soils (4.35 × 10(-5)± 1.00 × 10(-5) copies/16S rDNA), while those of sul2 exceeded the ones in non-irrigated soils still by a factor of 22 (6.61 × 10(-4) ± 0.59 × 10(-4) versus 2.99 × 10(-5) ± 0.26 × 10(-5) copies/16S rDNA). Absolute numbers of sul genes continued to increase with prolonging irrigation together with Enterococcus spp. 23S rDNA and total 16S rDNA contents. Increasing total concentrations of antibiotics in soil are not accompanied by increasing relative abundances of resistance genes. Nevertheless, wastewater irrigation enlarges the absolute concentration of resistance genes in soils due to a long-term increase in total microbial biomass.

The soil environment is a primary component of the global biogeochemical sulfur (S) cycle, acting as a source and sink of various S species and mediating oxidation state changes. However, ecological significance of the various S forms and the impacts of human intervention and climate on the amount and structural composition of these compounds are still poorly understood. We investigated the long-term influences of anthropogenically mediated transitions from natural to managed ecosystems on molecular-level speciation, biogeochemical dynamics, and the apparent temperature sensitivity of S moieties in temperate, subtropical, and tropical environments with mean annual temperature (MAT) ranging from 5 degrees C to 21 degrees C, using elemental analysis and X-ray absorption near-edge structure (XANES) spectroscopy. Land-use and land-cover changes led to the depletion of total soil S in all three ecoregions over a period of up to 103 years. The largest decline occurred from tropical forest agroecosystems (67% Kakamega and 76% Nandi, Kenya), compared to losses from temperate (36% at Lethbridge, Canada, and 40% at Pendleton, USA) and subtropical (48% at South Africa) grassland agroecosystems. The total S losses correlated significantly with MAT. Anthropogenic interventions profoundly altered the molecular-level composition and resulted in an apparent shift in oxidation states of organic S from native ecosystems composed primarily of S moieties in intermediate and highly reduced oxidation states toward managed agroecosystems dominated by organic S rich in strongly oxidized functionalities. The most prominent change occurred in thiols and sulfides, the proportion of which decreased by 46% (Lethbridge) and 57% (Pendleton) in temperate agroecosystems, by 46% in subtropical agroecosystems, and by 79% (Nandi) and 81% (Kakamega) in tropical agroecosystems. The proportion of organic S directly linked to O increased by 81%, 168%, 40%, 92%, and 85%, respectively. Among the various organic S functionalities, thiols and sulfides seem to have higher apparent temperature sensitivity, and thus these organic S moieties may become prone to losses due to land-use changes, even from the cooler regions of the world if MAT of these regions rise in the future.

Tropical and temperate soils differ with respect to their chemical conditions and mineral composition. Consequently, assessment of the contamination of tropical soils with pesticides requires methods that provide exhaustive extraction from the specific soil matrix and reliable quantification. Our objective was to optimize the simultaneous extraction and determination of 32 representative pesticides (organophosphates, organochlorines, synthetic pyrethroids, triazines, acetamides, carbamates, diphenyl ethers, acylalanines, oxadiazoles, thiadiazoles, and phenoxy compounds) frequently used in Thailand. The compounds were added to a clayey Ultisol-topsoil (45% clay) from the Yom Region in Northern Thailand. Ten different solvent mixtures were tested; the use of a shake extraction with acetone-ethyl acetate-water (3 + 1 + 1, v/v/v) was most effective in providing exhaustive and reproducible extraction of pesticides both from freshly fortified soil and from fortified soil after incubation for 14-28 days. The pesticides were separated and quantified by using gas chromatography with mass selective detection. Except for methamidophos, which was almost completely lost during sample workup, the recoveries of all pesticides from soil ranged from 68.6 to 104% (mean standard error, 2.8%) for freshly spiked samples and from 45.9 to 107% (mean standard error, 2.3%) for spiked samples incubated for 14 days. The use of internal standards compensated for the losses of most pesticides during workup and increased the mean recovery of the pesticides from freshly fortified soil to 96%. The method was successfully applied to the determination of environmental concentrations of pesticides in a range of Thai agricultural soils.

The efficacy and fate of pesticides in soil strongly depend on sorption reversibility that is known to decrease with increasing contact time (aging). We elucidated the aging dynamics of eight different pesticides in two contrasting agricultural soils of tropical Brazil (Ustox and Psamments), using batch equilibrium experiments and sequential extractions of field samples. Adsorption was best described by Langmuir isotherms for the entire and by Freundlich equations for the lower concentration range. In field samples, water extractable pesticide fractions mostly dissipated at least twice as fast as did the solvent extractable fractions. Hence, in comparison to 0 days K(OC) values, measured field K(OC) values were higher by a factor of 2.6-38 for the clayey Ustox and 2.1-72 for the sandy Psamments toward the end of the experimental period at 80 days after application. The extent of such aging basically increased with increasing polarity of the pesticide. An absolute enrichment of polar pesticides within the final exhaustive acetone--ethyl acetate--water extracts was observed during the experimental period, so that we may deduce that pesticides had redistributed into stronger sorption sites. The time course of the K(OC) development was well-described using a semiempirical equation, which had been employed for temperate soils before.

There may be important biological sources of polycyclic aromatic hydrocarbons (PAHs) to the global environment, particularly of naphthalene, phenanthrene, and perylene, that originate in the tropics. We (i) studied the distribution of PAHs among different compartments of a typical Cerrado to locate their sources and (ii) quantified the PAH storage of this ecosystem. The sum of 20 PAH (sigma20PAHs) concentrations ranged from 25 to 666 microg kg(-1) in plant tissue, 7.4 to 32 microg kg(-1) in litterfall, 206 to 287 microg kg(-1) in organic soil, and 10 to 79 microg kg(-1) in mineral soil. Among the living biomass compartments, the bark had the highest mean PAH concentrations and coarse roots the lowest, indicating that PAHs in the plants originated mainly from aboveground sources. Naphthalene and phenanthrene were the most abundant individual PAHs, together contributing 33 to 96% to the sigma20PAHs concentrations. The total storage of the X20PAHs in Cerrado was 7.5 mg m(-2) to a 0.15-m soil depth and 49 mg m(-2) to a 2-m soil depth. If extrapolated to the entire Brazilian Cerrado region, roughly estimated storages of naphthalene and phenanthrene correspond to 7300 and 400 yr of the published annual emissions in the United Kingdom, respectively. The storage of benzo[a]pyrene, a typical marker for fossil fuel combustion, in the Cerrado only corresponds to 0.19 yr of UK emissions. These results indicate that the Brazilian savanna comprises a huge reservoir of naphthalene and phenanthrene originating most likely from the aboveground parts of the vegetation or associated organisms. Thus, the Cerrado might be a globally important source of these PAHs.

The dissipation rate of seven currently used soybean and corn pesticides in two tropical soils (Ustox and Psamments) of Brazil was studied in a laboratory incubation experiment. Dissipation half-lives of pesticides ranged between 2 (monocrotofos) and 90 days (endosulfan-beta). The contrasting clay contents of the studied tropical soils (130 versus 470 g of clay kg(-1) of soil) did not influence the dissipation dynamics of pesticides substantially. Mineralization to CO(2) was high [up to 78% of the applied radioactivity (AR)] for the studied organophosphorus compounds and deltamethrin, which also formed considerable amounts of bound residues (>20% of AR) during the 80 days of incubation. The highest portion of nonextractable residues was found for alachlor and simazine (55-60% of AR). In contrast, the nonpolar trifluralin and endosulfan formed only small amounts of bound residues (mostly <20% of AR) but showed the highest dissipation half-lives (>14 days) in the studied soils, also due to a low mineralization rate. When endosulfan-sulfate, as the main metabolite of endosulfan, was considered, the half-life time of endosulfan compounds (sum of -alpha, -beta, and -sulfate) was enhanced to >160 days in both soils. In comparison with the laboratory experiments, dissipation half-life times of chlorpyrifos, endosulfan-alpha, and trifluralin were shortened by a factor of 10-30 in field trials with the same soils, which was related to the volatilization potential of pesticides from soils.

The application of a combined gas chromatography-combustion/isotope ratio mass spectrometry (GC-C/IRMS) method for stable carbon isotope analysis of amino acid enantiomers in soil samples is presented. Triplicate delta(13)C analyses of pentafluoropropionyl (PFP) isopropyl ester derivatives of 27 amino acid enantiomers revealed that discrimination of (13)C during derivatization is different for different amino acid enantiomers and different amounts. Injection of increasing amounts of amino acid derivatives showed that the isotopic signal varied up to 10 per thousand for D-aspartic acid. Correction for the delta(13)C signal of underivatized amino acid enantiomers is possible for all investigated amino acid enantiomers using logarithmic functions. Operating the GC-C/IRMS system in the split-mode (split ratio 1:12) is possible but resulted in a higher isotopic discrimination. The detection limit approached 3 ng for some amino acid enantiomers in the splitless mode, while the lower limit of routine determination exceeded 10 ng injection amount. The upper limit at which accurate stable isotope values were obtained was 200 ng injection amount. Compound-specific delta(13)C analysis of alanine, valine, aspartic and glutamic acid showed that the D-forms were enriched in (13)C relative to the L-forms, suggesting that microbes significantly contributed to the formation of the D-enantiomers in soil., (Copyright 2002 John Wiley & Sons, Ltd.)

Abstract The cycling of iron (Fe) is often closely linked with that of carbon, nitrogen, phosphorus and manganese. Therefore, alterations in the Fe cycle may be indicative of concurrent overall changes in the biogeochemistry of terrestrial and aquatic ecosystems. Biogeochemical processes taking part in the Fe cycle frequently fractionate stable Fe isotopes, leaving soil, plant and other compartments of the ecosystems with varied Fe isotopic signatures. In this work, we reviewed the Fe isotope fractionation processes that have been reported so far for terrestrial ecosystems. While parent materials vary in Fe isotope compositions, pedogenic processes can further fractionate Fe isotope signatures, resulting in soil profiles with δ56Fe values (relative to isotope standard IRMM-014) from −0.52 to +0.72‰. Different soil Fe pools, as a result of cycling processes, show an even broader range of δ56Fe values, with secondary Fe oxides being isotopically the lightest, and with Fe sequestered in silicate minerals being the heaviest, due to preferential release of light Fe isotopes during dissolution of minerals. Actually and potentially plant-available Fe in soil can be extracted by 0.5 M HCl, which includes pools of water-extractable and exchangeable Fe, organically bound or adsorbed Fe, and poorly crystalline Fe oxides, altogether showing a depletion of heavy Fe isotopes with δ56Fe values down to −1.08‰. Depending on the Fe speciation and concentration present in the growth medium, plants can adapt their uptake strategy for Fe. Plants of the strategy I type especially take up light iron isotopes, while strategy II plants fractionate less towards light isotopes. Aboveground tissues usually show lighter Fe isotope signatures than the roots, with flowers (δ56Fe: −2.15 to −0.23‰) being isotopically the lightest. In freshwater systems, the most distinct Fe isotope fractionation is usually found at the oxic-anoxic interface, where redox conditions change and thus Fe speciation controls the degree of Fe isotope fractionation. Similar to soils, the δ56Fe values of unfiltered water mainly reflect averaged Fe isotope compositions across fractions with different particle sizes. In filtered freshwater (<0.45 μm), isolated colloid-sized fractions can exhibit either positive or negative δ56Fe values, depending on the chosen size fraction and the origin of the (nano) particles, with δ56Fe values up to +2.79‰ for fractions smaller than 0.003 μm from an arctic stream or down to −1.73‰ for dissolved Fe (<0.02 μm) from a boreal forested catchment. Most freshwater studies showed that rivers with elevated contents of dissolved organic carbon (DOC) tend to be isotopically heavier than those with lower DOC contents, while some studies also showed that rivers with high DOC can display light Fe isotopic signatures owing to the input of groundwater- and/or soil water-derived Fe. Finally, anthropogenic impacts can contribute to Fe isotope fractionation in freshwaters and may widen the range of δ56Fe values in the environment, with the lowest records found down to −5.29‰. Overall, our compilation reveals that Fe pools in different terrestrial system compartments vary in stable Fe isotope compositions, although the current database is still small. In order to use stable Fe isotopes as proxies to reconstruct the biogeochemical processes, future works should not solely rely on bulk δ56Fe assessments, but also involve the assessment of different fractionation factors for all biogeochemical pathways, which includes isotopic analyses among various pools of the terrestrial Fe cycle. [ABSTRACT FROM AUTHOR]

Understanding and quantification of phosphorus (P) fluxes are key requirements for predictions of future forest ecosystems changes as well as for transferring lessons learned from natural ecosystems to croplands and plantations. This review summarizes and evaluates the recent knowledge on mechanisms, magnitude, and relevance by which dissolved and colloidal inorganic and organic P forms can be translocated within or exported from forest ecosystems. Attention is paid to hydrological pathways of P losses at the soil profile and landscape scales, and the subsequent influence of P on aquatic ecosystems. New (unpublished) data from the German Priority Program 1685 ' Ecosystem Nutrition: Forest Strategies for limited Phosphorus Resources' were added to provide up-to-date flux-based information. Nitrogen (N) additions increase the release of water-transportable P forms. Most P found in percolates and pore waters belongs to the so-called dissolved organic P (DOP) fractions, rich in orthophosphate-monoesters and also containing some orthophosphate-diesters. Total solution P concentrations range from ca. 1 to 400 µg P L−1, with large variations among forest stands. Recent sophisticated analyses revealed that large portions of the DOP in forest stream water can comprise natural nanoparticles and fine colloids which under extreme conditions may account for 40-100% of the P losses. Their translocation within preferential flow passes may be rapid, mediated by storm events. The potential total P loss through leaching into subsoils and with streams was found to be less than 50 mg P m−2 a−1, suggesting effects on ecosystems at centennial to millennium scale. All current data are based on selected snapshots only. Quantitative measurements of P fluxes in temperate forest systems are nearly absent in the literature, probably due to main research focus on the C and N cycles. Therefore, we lack complete ecosystem-based assessments of dissolved and colloidal P fluxes within and from temperate forest systems. [ABSTRACT FROM AUTHOR]

Veterinary antibiotics entering agricultural land with manure pose the risk of spreading antibiotic resistance. The fate of sulfadiazine ( SDZ) introduced via manure and its effect on resistance gene levels in the rhizosphere were compared with that in bulk soil. Maize plants were grown for 9 weeks in soil fertilized with manure either from SDZ-treated pigs ( SDZ treatment) or from untreated pigs (control). CaCl2-extractable concentrations of SDZ dissipated faster in the rhizosphere than in bulk soil, but SDZ remained detectable over the whole time. For bulk soil, the abundance of sul1 and sul2 relative to 16S r RNA gene copies was higher in the SDZ treatment than in the control, as revealed by quantitative PCR on days 14 and 63. In the rhizosphere, sampled on day 63, the relative sul gene abundances were also significantly increased in the SDZ treatment. The accumulated SDZ exposure (until day 63) of the bacteria significantly correlated with the log relative abundance of sul1 and sul2, so that these resistance genes were less abundant in the rhizosphere than in bulk soil. Plasmids conferring SDZ resistance, which were exogenously captured in Escherichia coli, mainly belonged to the Low GC group and carried a heterogeneous load of resistances to different classes of antibiotics. [ABSTRACT FROM AUTHOR]

Abstract: To distinguish between pyrogenic and biological sources of PAHs in a tropical rain forest near Manaus, Brazil, we determined the concentrations of 21 PAHs in leaves, bark, twigs, and stem wood of forest trees, dead wood, mineral topsoil, litter layer, air, and Nasutitermes termite nest compartments. Naphthalene (NAPH) was the most abundant PAH with concentrations of 35ngm-3 in air (>85% of the ∑21PAHs concentration), up to 1000μgkg-1 in plants (>90%), 477μgkg-1 in litter (>90%), 32μgkg-1 in topsoil (>90%), and 160μgkg-1 (>55%) in termite nests. In plants, the concentrations of PAHs in general decreased in the order leaves>bark>twigs>stem wood. The concentrations of most low-molecular weight PAHs in leaves and bark were near equilibrium with air, but those of NAPH were up to 50 times higher. Thus, the atmosphere seemed to be the major source of all PAHs in plants except for NAPH. Additionally, phenanthrene (PHEN) had elevated concentrations in bark and twigs of Vismia cayennensis trees (12–60μgkg-1), which might have produced PHEN. In the mineral soil, perylene (PERY) was more abundant than in the litter layer, probably because of in situ biological production. Nasutitermes nests had the highest concentrations of most PAHs in exterior compartments (on average 8 and 15μgkg-1 compared to <3μgkg-1 in interior parts) and high PERY concentrations in all compartments (12–86μgkg-1), indicating an in situ production of PERY in the nests. Our results demonstrate that the deposition of pyrolytic PAHs from the atmosphere controls the concentrations of most PAHs. However, the occurrence of NAPH, PHEN, and PERY in plants, termite nests, and soils at elevated concentrations supports the assumption of their biological origin. [Copyright &y& Elsevier]

Abstract: This review summarizes current knowledge about the interplay between fate and effects of the antibiotic sulfadiazine in soil ecosystems. In applying manure from antibiotic-treated animals to arable soils, sulfadiazine can reach the environment, but fate and transformation processes and the consequences for soil microorganisms and soil functions have not been studied adequately. Since antibiotics are explicitly designed to affect microorganisms, they are likely to affect “non-target” microbes in the soil ecosystem. Recent papers provide new insights into the disappearance dynamics of sulfadiazine, its effects on distinct microbial communities and the development of antibiotic resistance. [Copyright &y& Elsevier]