Natural farming improves crop yield in SE India when compared to conventional or organic systems by enhancing soil quality.

Zero Budget Natural Farming (ZBNF) is a grassroot agrarian movement and a state backed extension in Andhra Pradesh, and has been claimed to potentially meet the twin goals of global food security and environmental conservation. However, there is a lack of statistically evaluated data to support assertions of yield benefits of ZBNF compared to organic or conventional alternatives, or to mechanistically account for them. In order to fill this gap, controlled field experiments were established in twenty-eight farms across six districts, spanning over 800 km, over three cropping seasons. In these experiments, we compared ZBNF (no synthetic pesticides or fertilisers, home-made inputs comprising desi cow dung and urine with mulch) to conventional (synthetic fertilisers and pesticides) and organic (no synthetic pesticides or fertilisers, no mulch, purchased organic inputs, e.g. farmyard manure and vermicompost) treatments, all with no tillage. Comparisons were made in terms of yield, soil pH, temperature, moisture content, nutrient content and earthworm abundance. Our data shows that yield was significantly higher in the ZBNF treatment (z score = 0.58 ± 0.08), than the organic (z= -0.34 ± 0.06) or conventional (-0.24 ± 0.07) treatment when all farm experiments were analysed together. However, the efficacy of the ZBNF treatment was context specific and varied according to district and the crop in question. The ZBNF yield benefit is likely attributed to mulching, generating a cooler soil, with a higher moisture content and a larger earthworm population. There were no significant differences between ZBNF and the conventional treatment in the majority of nutrients. This is a particularly important observation, as intensive use of synthetic pesticides and fertilisers comes with a number of associated risks to farmers' finances, human health, greenhouse gas emissions, biodiversity loss and environmental pollution. However, long-term field and landscape scale trials are needed to corroborate these initial observations. Supplementary Information: The online version contains supplementary material available at 10.1007/s13593-023-00884-x.

Effects of application of horticultural soil amendments on decomposition, quantity, stabilisation and quality of soil carbon.

Application of organic soil amendments is commonplace in horticulture to improve soil fertility. Whether this practice can also augment the soil carbon (C) pool has been of increasing interest in recent years. We used a controlled field experiment that has received annual applications of six different horticultural soil amendments for seven consecutive years. Each amendment was examined in terms of its contribution to bulk C and the distribution of C between theoretical pools, as defined by physical fractionation. Physical fractionation was combined with 13C nuclear magnetic resonance spectroscopy with cross-polarization and magic angle spinning (CPMAS NMR) analysis. Results indicated that the difference in total C concentration between treatments resulted from an increase in unprotected, free, particulate organic matter (fOM), rather than an increase in soil organic matter being occluded in aggregates or in organo-mineral complexes, and that C persisted in the fOM fraction as a result of accumulation in the alkyl C region. Unlike fresh litter or plant residues, organic amendments have undergone decomposition during the composting process (or during formation in the case of peat), in the absence of mineral soil components. This ex situ decomposition (and possible stabilization through acquired recalcitrance) could reduce the opportunity to become physically or chemically protected through association with the soil mineral phase following addition to soil. Carbon:Nitrogen (C:N) of amendment material likely influenced the rate of amendment decomposition. In addition, C:N determines the decomposition of plant litter inputs, as determined by the tea bag index.

Building soil sustainability from root-soil interface traits.

Great potential exists to harness plant traits at the root-soil interface, mainly rhizodeposition and root hairs, to 'build' soils with better structure that can trap more carbon and resources, resist climate stresses, and promote a healthy microbiome. These traits appear to have been preserved in modern crop varieties, but scope exists to improve them further because they vary considerably between genotypes and respond to environmental conditions. From emerging evidence, rhizodeposition can act as a disperser, aggregator, and/or hydrogel in soil, and root hairs expand rhizosheath size. Future research should explore impacts of selecting these traits on plants and soils concurrently, expanding from model plants to commercial genotypes, and observing whether impacts currently limited to glasshouse studies occur in the field.

Ecotoxicity of oil sludges and residuals from their washing with surfactants: soil dehydrogenase and ryegrass germination tests.

Oil sludge washing (OSW) with surfactants and co-solvents is used to recover the oil, and this process leaves some residuals (sediments and surfactant solution). Currently, there are no data on the ecotoxicological effects of these OSW residuals from different sludges. This study evaluated the toxicity of OSW residuals from washing four types of oil sludges with five surfactants (Triton X-100 and X-114, Tween 80, sodium dodecyl sulphate (SDS) and rhamnolipid) and a co-solvent (cyclohexane). The toxicity of the residuals was evaluated with the impact on the soil microbial dehydrogenase activity (DHA) and ryegrass (Lolium perenne) seed germination. There was a high DHA detected directly in the sludges and all OSW residual combinations, but this activity could not be attributed to the DHA itself but to some chemical interferences. The DHA was then tested in the soils amended with the OSW residuals to simulate a bioremediation scenario. There were no chemical interferences in this case. In general, the INTF concentrations were significantly higher at low concentrations, 1 and 5% (p < 0.01). There were no significant differences in the DHA at high concentrations of OSW residuals (10, 25 and 50%) which implied that the concentration of the contaminants is not directly proportional to the levels of ecotoxicity. Unexpectedly, the INTF values of the 10, 25 and 50% rhamnolipid-OSW residuals were significantly lower than the Triton X-100 residuals. The ryegrass germination rates were higher than 70% with no apparent phytotoxicity symptoms in the seedlings. Particularly, there was a highly significant negative effect of the residuals on the germination rates at high concentrations (p < 0.01). Given that the extractable petroleum hydrocarbon (EPH) concentrations in the OSW residual-amended soils in both DHA and germination tests were very low (13-21 ppm), other co-contaminants could be contributing to the toxicity. These findings implied that biotreatment techniques can be applied to treat the OSW residuals if necessary.

Oil sludge washing with surfactants and co-solvents: oil recovery from different types of oil sludges.

Different physicochemical and biological treatments have been used to treat oil sludges, and oil recovery techniques are preferred such as oil sludge washing (OSW) with surfactants and co-solvents. Toluene is commonly used as co-solvent, but it is non-benign to the environment. This study tested alternative co-solvents (n-pentane, n-hexane, cyclohexane, and isooctane) at 1:1 and 2:1 C/OS (co-solvent to oil sludge ratio). Also, this study evaluated the effect on the oil recovery rate (ORR) of three main parameters in the washing: type, concentration, and application ratio (S/OS) of surfactants to oil sludges. To date, no study has assessed these parameters in the washing of oil sludges from different sources. Four types of oil sludges and five surfactants (Triton X-100 and X-114, Tween 80, sodium dodecyl sulphate (SDS), and rhamnolipid) were used. The results showed that cyclohexane had high ORR and could be used instead of toluene because it is more benign to the environment. The S/OS ratio had a high effect on the ORR and depended on the type of oil sludge. Rhamnolipid, Triton X-100, and Triton X-114 had the highest oil recovery rates (40 - 70%). In addition, it was found that the surfactant concentration had no effect on the ORR. Consequently, the addition of surfactant was not significantly different compared to the washing with no surfactants, except for one sludge. The use of the surfactant in the washing solution can help in the selective extraction of specific oil hydrocarbon fractions in the recovered oil to assess its potential reuse as fuel. Further recommendations were given to improve the OSW process.

Maximisation of oil recovery from an oil-water separator sludge: Influence of type, concentration, and application ratio of surfactants.

Worldwide the generation of oil sludges is approximately 160 million metric tonnes per annum. The washing of oil sludge with surfactant solutions can be used to recover the oil and reused as a feedstock for fuel production. There is a need to establish the influence of the surfactant type, concentration, and application (surfactant to oil sludge, S/OS) ratio to oil sludge for the maximisation of oil recovery. This study presented the oil recovery rates from the washing of an oil-water separator sludge using surfactants, Triton X-100, sodium dodecyl sulphate (SDS), Tween 80, rhamnolipid, and Triton X-114. The surfactants were characterised by critical micelle concentration (CMC), micelle size, and surface activity. A Taguchi experimental design was applied to reduce the number of experimental runs. In general, Triton X-100 and X-114, and rhamnolipid had higher micelle sizes and surfactant activities which resulted in higher oil recoveries. The key role of the surfactants in the washing was evidenced because the ORR values with the surfactants were significantly higher than the value with the control with no surfactant solution. The S/OS ratio was the factor with the largest effect on the Taguchi signal-to-noise ratio (an indicator of variation) of the oil recovery rate. The levels with the maximum recovery rate were 1:1 S/OS, 2CMC of surfactant concentration and Triton X-100 (32% ±â€¯5), Triton X-114 (30% ±â€¯7), and rhamnolipid (29% ±â€¯8). In conclusion, less surfactant solution (1:1 S/OS) and low surfactant concentration (≤2CMC) provided the maximum oil recovery from this type of oil sludge. To our knowledge, no previous study with surfactants has reported low oil recovery values at high S/OS ratios in the oil sludge washing.

Bioaccessibility of PBDEs present in indoor dust: A novel dialysis membrane method with a Tenax TA® absorption sink.

Human uptake of flame retardants (FRs) such as polybrominated diphenyl ethers (PBDEs) via indoor dust ingestion is commonly considered as 100% bioaccessible, leading to potential risk overestimation. Here, we present a novel in vitro colon-extended physiologically-based extraction test (CE-PBET) with Tenax TA® as an absorptive "sink" capable to enhance PBDE gut bioaccessibility. A cellulose-based dialysis membrane (MW cut-off 3.5kDa) with high pH and temperature tolerance was used to encapsulate Tenax TA®, facilitating efficient physical separation between the absorbent and the dust, while minimizing re-absorption of the ingested PBDEs to the dust particles. As a proof of concept, PBDE-spiked indoor dust samples (n=3) were tested under four different conditions; without any Tenax TA® addition (control) and with three different Tenax TA® loadings (i.e. 0.25, 0.5 or 0.75g). Our results show that in order to maintain a constant sorptive gradient for the low MW PBDEs, 0.5g of Tenax TA® are required in CE-PBET. Tenax TA® inclusion (0.5g) resulted in 40% gut bioaccessibility for BDE153 and BDE183, whereas greater bioaccessibility values were seen for less hydrophobic PBDEs such as BDE28 and BDE47 (~60%). When tested using SRM 2585 (n=3), our new Tenax TA® method did not present any statistically significant effect (p>0.05) between non-spiked and PBDE-spiked SRM 2585 treatments. Our study describes an efficient method where due to the sophisticated design, Tenax TA® recovery and subsequent bioaccessibility determination can be simply and reliably achieved.

Legacy and alternative flame retardants in Norwegian and UK indoor environment: Implications of human exposure via dust ingestion.

Indoor dust has been acknowledged as a major source of flame retardants (FRs) and dust ingestion is considered a major route of exposure for humans. In the present study, we investigated the presence of PBDEs and alternative FRs such as emerging halogenated FRs (EHFRs) and organophosphate flame retardants (PFRs) in indoor dust samples from British and Norwegian houses as well as British stores and offices. BDE209 was the most abundant PBDE congener with median concentrations of 4700ngg-1 and 3400ngg-1 in UK occupational and house dust, respectively, 30 and 20 fold higher than in Norwegian house dust. Monomeric PFRs (m-PFRs), including triphenyl phosphate (TPHP), tris(chloropropyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) dominated all the studied environments. To the best of our knowledge, this is the first report of isodecyldiphenyl phosphate (iDPP) and trixylenyl phosphate (TXP) in indoor environments. iDPP was the most abundant oligomeric PFR (o-PFR) in all dust samples, with median concentrations one order of magnitude higher than TXP and bisphenol A bis(diphenyl phosphate (BDP). iDPP and TXP worst-case scenario exposures for British workers during an 8h exposure in the occupational environment were equal to 34 and 1.4ngkgbw-1day-1, respectively. The worst-case scenario for BDE209 estimated exposure for British toddlers (820ngkgbw-1day-1) did not exceeded the proposed reference dose (RfD) (7000ngkgbw-1day-1), while exposures for sum of m-PFRs (Σm-PFRs) in British toddlers and adults (17,900 and 785ngkgbw-1day-1 respectively) were an order of magnitude higher than for Norwegian toddlers and adults (1600 and 70ngkgbw-1day-1).

Modelling the bioaccumulation of persistent organic pollutants in agricultural food chains for regulatory exposure assessment.

New models for estimating bioaccumulation of persistent organic pollutants in the agricultural food chain were developed using recent improvements to plant uptake and cattle transfer models. One model named AgriSim was based on K OW regressions of bioaccumulation in plants and cattle, while the other was a steady-state mechanistic model, AgriCom. The two developed models and European Union System for the Evaluation of Substances (EUSES), as a benchmark, were applied to four reported food chain (soil/air-grass-cow-milk) scenarios to evaluate the performance of each model simulation against the observed data. The four scenarios considered were as follows: (1) polluted soil and air, (2) polluted soil, (3) highly polluted soil surface and polluted subsurface and (4) polluted soil and air at different mountain elevations. AgriCom reproduced observed milk bioaccumulation well for all four scenarios, as did AgriSim for scenarios 1 and 2, but EUSES only did this for scenario 1. The main causes of the deviation for EUSES and AgriSim were the lack of the soil-air-plant pathway and the ambient air-plant pathway, respectively. Based on the results, it is recommended that soil-air-plant and ambient air-plant pathway should be calculated separately and the K OW regression of transfer factor to milk used in EUSES be avoided. AgriCom satisfied the recommendations that led to the low residual errors between the simulated and the observed bioaccumulation in agricultural food chain for the four scenarios considered. It is therefore recommended that this model should be incorporated into regulatory exposure assessment tools. The model uncertainty of the three models should be noted since the simulated concentration in milk from 5th to 95th percentile of the uncertainty analysis often varied over two orders of magnitude. Using a measured value of soil organic carbon content was effective to reduce this uncertainty by one order of magnitude.

Alkali-earth metal bridges formed in biofilm matrices regulate the uptake of fluoroquinolone antibiotics and protect against bacterial apoptosis.

Bacterially extracellular biofilms play a critical role in relieving toxicity of fluoroquinolone antibiotic (FQA) pollutants, yet it is unclear whether antibiotic attack may be defused by a bacterial one-two punch strategy associated with metal-reinforced detoxification efficiency. Our findings help to assign functions to specific structural features of biofilms, as they strongly imply a molecularly regulated mechanism by which freely accessed alkali-earth metals in natural waters affect the cellular uptake of FQAs at the water-biofilm interface. Specifically, formation of alkali-earth-metal (Ca2+ or Mg2+) bridge between modeling ciprofloxacin and biofilms of Escherichia coli regulates the trans-biofilm transport rate of FQAs towards cells (135-nm-thick biofilm). As the addition of Ca2+ and Mg2+ (0-3.5 mmol/L, CIP: 1.25 µmol/L), the transport rates were reduced to 52.4% and 63.0%, respectively. Computational chemistry analysis further demonstrated a deprotonated carboxyl in the tryptophan residues of biofilms acted as a major bridge site, of which one side is a metal and the other is a metal girder jointly connected to the carboxyl and carbonyl of a FQA. The bacterial growth rate depends on the bridging energy at anchoring site, which underlines the environmental importance of metal bridge formed in biofilm matrices in bacterially antibiotic resistance.

Does the source migration pathway of HBCDs to household dust influence their bio-accessibility?

A study was conducted to assess the human bioaccessibility of dust contaminated with hexabromocyclododecane (HBCD) via two migration pathways a) volatilisation with subsequent partitioning to dust particles, and b) abrasion of treated textile fibres directly to the dust. This was achieved using previously developed experimental chamber designs to generate dust samples contaminated with HBCDs emitted from a HBCD treated textile curtain. The generated dust samples were exposed to an in vitro colon extended physiologically based extraction test (CE-PBET). The bioaccessibility of the HBCDs which were incorporated within dust as a result of volatilisation from the curtain material with subsequent partitioning to dust was higher than in dusts contaminated with HBCDs via abrasion of the curtain (35% and 15% respectively). We propose this occurs due to a stronger binding of HBCDs to treated fabric fibres than that experienced following volatilisation and sorption of HBCDs to dust particles.

Considering evidence: The approach taken by the Hazardous Substances Advisory Committee in the UK.

The Hazardous Substances Advisory Committee (HSAC) provides expert advice to UK officials, Ministers and other relevant bodies on the protection of the environment, and human health via the environment, from potentially hazardous substances and articles. Hazardous substances are often the subject of controversy, on which individuals, and different groups in society, hold divergent views. This paper details the approach taken by HSAC when considering the evidence to provide advice on hazardous substances. Firstly HSAC reviews the range of evidence and determines its quality considering: transparency of aims, the methodology and results, completeness, independent review and accessibility. HSAC does not follow one explicit methodology as the wide range of hazardous substances we consider means they need to be addressed on a case by case basis. Most notably HSAC considers the evidence in the wider context, being aware of factors that influence individuals in their decision making when receiving a HSAC opinion e.g. trust in the source of the evidence, defensibility, conformity to a 'world view' and framing. HSACs also reflect on its own perspectives with the aim of addressing bias by the diversity of its membership. The Committee's intention, in adopting this rounded approach, is to reach opinions that are robust, relevant and defensible.

Assessment and improvement of biotransfer models to cow's milk and beef used in exposure assessment tools for organic pollutants.

The aim of this study was to assess and improve the accuracy of biotransfer models for the organic pollutants (PCBs, PCDD/Fs, PBDEs, PFCAs, and pesticides) into cow's milk and beef used in human exposure assessment. Metabolic rate in cattle is known as a key parameter for this biotransfer, however few experimental data and no simulation methods are currently available. In this research, metabolic rate was estimated using existing QSAR biodegradation models of microorganisms (BioWIN) and fish (EPI-HL and IFS-HL). This simulated metabolic rate was then incorporated into the mechanistic cattle biotransfer models (RAIDAR, ACC-HUMAN, OMEGA, and CKow). The goodness of fit tests showed that RAIDAR, ACC-HUMAN, OMEGA model performances were significantly improved using either of the QSARs when comparing the new model outputs to observed data. The CKow model is the only one that separates the processes in the gut and liver. This model showed the lowest residual error of all the models tested when the BioWIN model was used to represent the ruminant metabolic process in the gut and the two fish QSARs were used to represent the metabolic process in the liver. Our testing included EUSES and CalTOX which are KOW-regression models that are widely used in regulatory assessment. New regressions based on the simulated rate of the two metabolic processes are also proposed as an alternative to KOW-regression models for a screening risk assessment. The modified CKow model is more physiologically realistic, but has equivalent usability to existing KOW-regression models for estimating cattle biotransfer of organic pollutants.

'Towards a unified approach for the determination of the bioaccessibility of organic pollutants'.

Bioaccessibility studies have been widely used as a research tool to determine the potential human exposure to ingested contaminants. More recently they have been practically applied for soil borne toxic elements. This paper reviews the application of bioaccessibility tests across a range of organic pollutants and contaminated matrices. Important factors are reported to be: the physiological relevance of the test, the components in the gut media, the size fraction chosen for the test and whether it contains a sorptive sink. The bioaccessibility is also a function of the composition of the matrix (e.g. organic carbon content of soils) and the physico-chemical characteristics of the pollutant under test. Despite the widespread use of these tests, there are a large number of formats used and very few validation studies with animal models. We propose a unified format for a bioaccessibility test for organic pollutants. The robustness of this test should first be confirmed through inter laboratory comparison, then tested in-vivo.

Assessment of plant uptake models used in exposure assessment tools for soils contaminated with organic pollutants.

The aim of this study was to evaluate and improve the accuracy of plant uptake models for neutral hydrophobic organic pollutants (1 < logK(OW) < 9, -8 < logK(AW) < 0) used in regulatory exposure assessment tools, using uncertainty and sensitivity analyses. The models considered were RAIDAR, EUSES, CSOIL, CLEA, and CalTOX. In this research, CSOIL demonstrated the best performance of all five exposure assessment tools for root uptake from polluted soil in comparison with observed data, but no model predicted shoot uptake well. Recalibration of the transpiration and volatilisation parameters improved the performance of CSOIL and CLEA. The dominant pathway for shoot uptake simulated differed according to the properties of the chemical under consideration; those with a higher air-water partition coefficient were transported into shoots via the soil-air-plant pathway, while chemicals with a lower octanol-water partition coefficient and air-water partition coefficient were transported via the root. The soil organic carbon content was a particularly sensitive parameter in each model and using a site specific value improved model performance.

Sorptive physiologically based extraction of contaminated solid matrices: incorporating silicone rod as absorption sink for hydrophobic organic contaminants.

The oral bioaccessibility of soil contaminants is increasingly assessed with physiologically based extraction tests (PBETs): the contaminant fraction that is desorbed into simulated digestive fluids is measured and classified as bioaccessible. However, this approach can lead to underestimations if the capacity of the fluids is insufficient to provide infinite sink conditions. Desorption will then progressively decrease and finally stop when equilibrium between soil and medium is reached. To circumvent this artifact, we incorporated a silicone rod as an absorption sink into the PBET to continuously absorb mobilized contaminants and maintain the desorption gradient. Polycyclic aromatic hydrocarbons served as model contaminants and the colon extended PBET as the extraction model. The inclusion of the silicone rod sink (1) increased the extraction capacity of the test by orders of magnitude, (2) ensured near infinite sink conditions, and (3) allowed for simple back-extraction of PAHs for their quantification by GC-MS. The silicone rod provided fast enrichment when applied to the stomach and small intestine compartment, but was somewhat slower in the richer colon compartment. Finally, the sorptive-PBET was applied to wood soot and a kindergarten soil. The present article provides the basis for how an absorption sink can be integrated into PBET models.

Nanoscale zerovalent iron alters soil bacterial community structure and inhibits chloroaromatic biodegradation potential in Aroclor 1242-contaminated soil.

Nanoscale zerovalent iron (nZVI) has potential for the remediation of organochlorine-contaminated environments. Environmental safety concerns associated with in situ deployment of nZVI include potential negative impacts on indigenous microbes whose biodegradative functions could contribute to contaminant remediation. With respect to a two-step polychlorinated biphenyl remediation scenario comprising nZVI dechlorination followed by aerobic biodegradation, we examined the effect of polyacrylic acid (PAA)-coated nZVI (mean diameter = 12.5 nm) applied at 10 g nZVI kg(-1) to Aroclor-1242 contaminated and uncontaminated soil over 28 days. nZVI had a limited effect on Aroclor congener profiles, but, either directly or indirectly via changes to soil physico-chemical conditions (pH, Eh), nZVI addition caused perturbation to soil bacterial community composition, and reduced the activity of chloroaromatic mineralizing microorganisms. We conclude that nZVI addition has the potential to inhibit microbial functions that could be important for PCB remediation strategies combining nZVI treatment and biodegradation.

Passive samplers provide a better prediction of PAH bioaccumulation in earthworms and plant roots than exhaustive, mild solvent, and cyclodextrin extractions.

A number of extraction methods have been developed to assess polycyclic aromatic hydrocarbon (PAH) bioavailability in soils. As these methods are rarely tested in a comparative manner, against different test organisms, and using field-contaminated soils, it is unclear which method gives the most accurate measure of the actual soil ecosystem exposure. In this study, PAH bioavailability was assessed in ten field-contaminated soils by using exhaustive acetone/hexane extractions, mild solvent (butanol) extractions, cyclodextrin extractions, and two passive sampling methods; solid phase micro extraction (SPME) and polyoxymethylene solid phase extraction (POM-SPE). Results were compared to actual PAH bioaccumulation in earthworms (Eisenia fetida) and rye grass (Lolium multiflorum) roots. Exhaustive, mild solvent and cyclodextrin extractions consistently overpredicted biotic concentrations by a factor of 10-10 000 and therefore seem inappropriate for predicting PAH bioaccumulation in field contaminated soils. In contrast, passive samplers generally predicted PAH concentrations in earthworms within a factor of 10, although correlations between predicted and measured concentrations were considerably scattered. The same applied to the plant data, where passive samplers also tended to underpredict root concentrations. These results indicate the potential of passive samplers to predict PAH bioaccumulation, yet call for comparative studies between passive samplers and further research on plant bioavailability.

Using deuterated PAH amendments to validate chemical extraction methods to predict PAH bioavailability in soils.

Validating chemical methods to predict bioavailable fractions of polycyclic aromatic hydrocarbons (PAHs) by comparison with accumulation bioassays is problematic. Concentrations accumulated in soil organisms not only depend on the bioavailable fraction but also on contaminant properties. A historically contaminated soil was freshly spiked with deuterated PAHs (dPAHs). dPAHs have a similar fate to their respective undeuterated analogues, so chemical methods that give good indications of bioavailability should extract the fresh more readily available dPAHs and historic more recalcitrant PAHs in similar proportions to those in which they are accumulated in the tissues of test organisms. Cyclodextrin and butanol extractions predicted the bioavailable fraction for earthworms (Eisenia fetida) and plants (Lolium multiflorum) better than the exhaustive extraction. The PAHs accumulated by earthworms had a larger dPAH:PAH ratio than that predicted by chemical methods. The isotope ratio method described here provides an effective way of evaluating other chemical methods to predict bioavailability.

Assessing the impact of nano- and micro-scale zerovalent iron particles on soil microbial activities: particle reactivity interferes with assay conditions and interpretation of genuine microbial effects.

The effects of nano-scale and micro-scale zerovalent iron (nZVI and mZVI) particles on general (dehydrogenase and hydrolase) and specific (ammonia oxidation potential, AOP) activities mediated by the microbial community in an uncontaminated soil were examined. nZVI (diameter 12.5 nm; 10 mg g⁻¹ soil) apparently inhibited AOP and nZVI and mZVI apparently stimulated dehydrogenase activity but had minimal influence on hydrolase activity. Sterile experiments revealed that the apparent inhibition of AOP could not be interpreted as such due to the confounding action of the particles, whereas, the nZVI-enhanced dehydrogenase activity could represent the genuine response of a stimulated microbial population or an artifact of ZVI reactivity. Overall, there was no evidence for negative effects of nZVI or mZVI on the processes studied. When examining the impact of redox active particles such as ZVI on microbial oxidation-reduction reactions, potential confounding effects of the test particles on assay conditions should be considered.