We evaluated how root-induced changes in rhizosphere pH varied and interacted with Cu availability and bioavailability in an acidic soil. Rape was grown on a Cu-contaminated acidic soil, which had been limed at 10 rates. Soil Cu bioavailability was not influenced by liming. However, liming significantly decreased CaCl2–extracted Cu for pH between 3.7 and 5.1. Little effect was found for pH above 5.1. For soil pH < 4.4, CaCl2–Cu contents were smaller in rhizosphere than uncropped soil. Rhizosphere alkalisation occurred at pH < 4.8, while acidification occurred at greater pH. This explained the changes of CaCl2–Cu in the rhizosphere at low pH and the absence of pH dependency of Cu bioavailability to rape. In addition, apoplastic Cu in roots increased with increasing soil pH, most probably as a result of increased dissociation and affinity of cell wall compounds for Cu. Root-induced increase in pH reduces Cu availability in the rhizosphere and Cu bioavailability to rape.

This study provides a coupled simulation-optimization approach for optimal design of petroleum-contaminated groundwater remediation under uncertainty. Compared to the previous approaches, it has the advantages of: (1) addressing the stochasticity of the modeling parameters in simulating the flow and transport of NAPLs in groundwater, (2) providing a direct and response-rapid bridge between remediation strategies (pumping rates) and remediation performance (contaminant concentrations) through the created proxy models, (3) alleviating the computational cost in searching for optimal solutions, and (4) giving confidence levels for the obtained optimal remediation strategies. The approach is applied to a practical site in Canada for demonstrating its performance. The results show that mitigating the effects of uncertainty on optimal remediation strategies (through enhancing the confidence level) would lead to the rise of remediation cost due to the increase in the total pumping rate. This study provides a coupled simulation-optimization approach for optimal design of groundwater remediation under uncertainty.

Zerovalent iron powder (ZVI or Fe⁰) and nanoparticulate ZVI (nZVI or nFe⁰) are proposed as cost-effective materials for the removal of aqueous antibiotics. Results showed complete removal of Amoxicillin (AMX) and Ampicillin (AMP) upon contact with Fe⁰ and nFe⁰. Antibiotics removal was attributed to three different mechanisms: (i) a rapid rupture of the β-lactam ring (reduction), (ii) an adsorption of AMX and AMP onto iron corrosion products and (iii) sequestration of AMX and AMP in the matrix of precipitating iron hydroxides (co-precipitation with iron corrosion products). Kinetic studies demonstrated that AMP and AMX (20 mg L⁻¹) undergo first-order decay with half-lives of about 60.3 ± 3.1 and 43.5 ± 2.1 min respectively after contact with ZVI under oxic conditions. In contrast, reactions under anoxic conditions demonstrated better degradation with t1/2 of about 11.5 ± 0.6 and 11.2 ± 0.6 min for AMP and AMX respectively. NaCl additions accelerated Fe⁰ consumption, shortening the service life of Fe⁰ treatment systems. 21Fe⁰ is efficient for the aqueous removal of the β-lactam antibiotics and chlorides enhanced the removal rate by sustaining the process of iron corrosion.

We examined the effect of ozone (O₃) on Norway spruce (Picea abies) needle epicuticular wax over three seasons at the Kranzberg Ozone Fumigation Experiment. Exposure to 2x ambient O₃ ranged from 64.5 to 74.2 μl O₃ l⁻¹ h AOT40, and 117.1 to 123.2 nl O₃ l⁻¹ 4th highest daily maximum 8-h average O₃ concentration. The proportion of current-year needle surface covered by wax tubes, tube aggregates, and plates decreased (P = 0.011) under 2x O₃. Epistomatal chambers had increased deposits of amorphous wax. Proportion of secondary alcohols varied due to year (P = 0.004) and O₃ treatment (P = 0.029). Secondary alcohols were reduced by 9.1% under 2x O₃. Exposure to 2x O₃ increased (P = 0.037) proportions of fatty acids by 29%. Opposing trends in secondary alcohols and fatty acids indicate a direct action of O₃ on wax biosynthesis. These results demonstrate O₃-induced changes in biologically important needle surface characteristics of 50-year-old field-grown trees. Free-air ozone exposure induced changes in needle wax characteristics of mature Picea abies.

The discharge of oil well produced water (PW) provides a constant source of contaminants to the marine environment including polycyclic aromatic hydrocarbons, alkylated phenols, metals and production chemicals. High concentrations of PW cause adverse effects to exposed biota, including reduced survival, growth and reproduction. Here we explore the effects of PW on immune function in the blue mussel, Mytilus edulis. Mussels were exposed for 21 days to sublethal PW concentrations (0.125-0.5%) and cellular parameters were measured. Cell viability, phagocytosis and cytotoxicity were inhibited after exposure to 0.25% and 0.5% PW, whilst the 0.125% PW treatment produced significant increases in these biomarker responses. This biphasic response was only observed after 7 days exposure; longer exposure periods led to a reduction in immune parameters. Results indicate that PW concentrations close to the discharge point cause modulation to cellular immunity. The implications for longer-term disease resistance are discussed. Exposure to produced water alters immune function in the sentinel species Mytilus edulis.

This paper evaluates approaches to calculate acceptable loads for metal deposition to forest ecosystems, distinguishing between critical loads, stand-still loads and target loads. We also evaluated the influence of including the biochemical metal cycle on the calculated loads. Differences are illustrated by examples of Cd, Cu, Pb and Zn for a deciduous forest on five major soil types in the Netherlands. Stand-still loads are generally lower than critical loads, which in turn are lower than the target loads indicating that present levels are below critical levels. Uncertainties in the calculated critical loads are mainly determined by the uncertainty in the critical limits and the chemical speciation model. Including the metal cycle has a small effect on the calculated critical loads. Results are discussed in view of the applicability of the critical load concept for metals in future protocols on the reduction in metal emissions. Critical load methods for metals can be used to assess future risks due to metal inputs.

Evaluation of the remediation ability of zinc/cadmium in hyper- and non-hyperaccumulator plant species through greenhouse studies is limited. To bridge the gap between greenhouse studies and field applications for phytoextraction, we used published data to examine the partitioning of heavy metals between plants and soil (defined as the bioconcentration factor). We compared the remediation ability of the Zn/Cd hyperaccumulators Thlaspi caerulescens and Arabidopsis halleri and the non-hyperaccumulators Nicotiana tabacum and Brassica juncea using a hierarchical linear model (HLM). A recursive algorithm was then used to evaluate how many harvest cycles were required to clean a contaminated site to meet Taiwan Environmental Protection Agency regulations. Despite the high bioconcentration factor of both hyperaccumulators, metal removal was still limited because of the plants' small biomass. Simulation with N. tabacum and the Cadmium model suggests further study and development of plants with high biomass and improved phytoextraction potential for use in environmental cleanup. A quantitative solution enables the evaluation of Zn/Cd phytoextraction.

In situ chemical oxidation is a commonly applied soil and groundwater remediation technology, but can have significant effects on soil properties, which in turn might affect fate and transport of organic contaminants. In this study, it was found that oxidation treatment resulted mainly in breakdown of soil organic matter (SOM) components. Sorption of naphthalene and phenanthrene to the original soils and the KMnO₄-treated soils was linear, indicating that hydrophobic partitioning to SOM was the predominant mechanism for sorption. Desorption from the original and treated soils was highly resistant, and was well modeled with a biphasic desorption model. Desorption of residual naphthalene after treating naphthalene-contaminated soils with different doses of KMnO4 also followed the biphasic desorption model very well. It appears that neither changes of soil properties caused by chemical oxidation nor direct chemical oxidation of contaminated soils had a noticeable effect on the nature of PAH-SOM interactions. Chemical oxidation of soils had little effect on the mechanisms controlling sorption and desorption of PAHs.

The degradation of a chiral nonylphenol isomer, 4-(1-ethyl-1,4-dimethylpentyl)phenol (NP₁₁₂), in two agricultural soils from Monheim and Dortmund, Germany has been studied. The degradation of NP₁₁₂ and the formation of a nitro-nonylphenol metabolite were determined by means of GC-MS analysis. The degradation followed bi-exponential order kinetics, with half-life of less than 5 days in both soils. The nitro-metabolite was found at different concentration levels in the two soils. The nitro-metabolite of NP₁₁₂ was more persistent than its parent compound. After 150 days about 13% of the initially applied NP₁₁₂ remained in the Monheim soil as its nitro-metabolite. Results of the E-screen assay revealed that the nitro-NP₁₁₂ has oestrogenic potency of 85% of that of NP₁₁₂. Furthermore, the results of chiral GC-MS analysis revealed that no chiral degradation of NP₁₁₂ occurred in this study. The degradation of a chiral nonylphenol isomer in agricultural soils followed bi-exponential order kinetics resulting in a more persistent nitro-metabolite.

Antibiotics are among the most successful drugs used for human therapy. However, since they can challenge microbial populations, they must be considered as important pollutants as well. Besides being used for human therapy, antibiotics are extensively used for animal farming and for agricultural purposes. Residues from human environments and from farms may contain antibiotics and antibiotic resistance genes that can contaminate natural environments. The clearest consequence of antibiotic release in natural environments is the selection of resistant bacteria. The same resistance genes found at clinical settings are currently disseminated among pristine ecosystems without any record of antibiotic contamination. Nevertheless, the effect of antibiotics on the biosphere is wider than this and can impact the structure and activity of environmental microbiota. Along the article, we review the impact that pollution by antibiotics or by antibiotic resistance genes may have for both human health and for the evolution of environmental microbial populations. The article reviews the current knowledge on the effects that pollution by antibiotics and antibiotic resistance genes may have for the microbiosphere.