Uptake and translocation of organophosphates and other emerging contaminants in food and forage crops

Emerging contaminants in wastewater and sewage sludge spread on agricultural soil can be transferred to the human food web directly by uptake into food crops or indirectly following uptake into forage crops. This study determined uptake and translocation of the organophosphates tris(1-chloro-2-propyl) phosphate (TCPP) (log K _ow 2.59), triethyl-chloro-phosphate (TCEP) (log K _ow 1.44), tributyl phosphate (TBP) (log K _ow 4.0), the insect repellent N,N-diethyl toluamide (DEET) (log K _ow 2.18) and the plasticiser N-butyl benzenesulfonamide (NBBS) (log K _ow 2.31) in barley, wheat, oilseed rape, meadow fescue and four cultivars of carrot. All species were grown in pots of agricultural soil, freshly amended contaminants in the range of 0.6–1.0 mg/kg dry weight, in the greenhouse. The bioconcentration factors for root (RCF), leaf (LCF) and seed (SCF) were calculated as plant concentration in root, leaf or seed over measured initial soil concentration, both in dry weight. The chlorinated flame retardants (TCEP and TCPP) displayed the highest bioconcentration factors for leaf and seed but did not show the same pattern for all crop species tested. For TCEP, which has been phased out due to toxicity but is still found in sewage sludge and wastewater, LCF was 3.9 in meadow fescue and 42.3 in carrot. For TCPP, which has replaced TCEP in many products and also occurs in higher residual levels in sewage sludge and wastewater, LCF was high for meadow fescue and carrot (25.9 and 17.5, respectively). For the four cultivars of carrot tested, the RCF range for TCPP and TCEP was 10–20 and 1.7–4.6, respectively. TCPP was detected in all three types of seeds tested (SCF, 0.015–0.110). Despite that DEET and NBBS have log K _ow in same range as TCPP and TCEP, generally lower bioconcentration factors were measured. Based on the high translocation of TCPP and TCEP to leaves, especially TCPP, into meadow fescue (a forage crop for livestock animals), ongoing risk assessments should be conducted to investigate the potential effects of these compounds in the food web.     

Temporal concentration changes of DEET,TCEP, terbutryn,and nonylphenols in freshwater streams of Hesse,Germany: possible influence of mandatory regulations and voluntary environmental agreements

Background, aim, and scope  

The present study focuses on the temporal concentration changes of four common organic pollutants in small freshwater streams of Hesse, Germany. The substances (tris(2-chloroethyl)phosphate (TCEP), the technical isomer mixture of 4-nonylphenol (NP), 2-(t-butylamino)-4-(ethylamino)-6-(methylthio)-s-triazine (terbutryn), and N,N-diethyl-m-toluamide (DEET)) are subject to differing regulations. Whereas the use of NP and the related nonylphenolethoxylates (NPEOs) are almost completely banned under EU directive 2003/53/EC, the herbicide terbutryn is only restricted for use as a herbicide in the majority of member states of the European Union (EU). In contrast, TCEP and DEET are not regulated by legislation, but have been replaced in some products through consumer pressure. The impact of regulation on the environmental concentrations of these pollutants is discussed.     

Influences of wetland plants on weathered acidic mine tailings

Establishment of Carex rostrata, Eriophorum angustifolium and Phragmites australis on weathered, acidic mine tailings (pH approximately 3) and their effect on pH in tailings were investigated in a field experiment. The amendments, sewage sludge and an ashes-sewage sludge mixture, were used as plant nutrition and their influence on the metal and As concentrations of plant shoots was analysed. An additional experiment was performed in greenhouse with E. angustifolium and sewage sludge as amendments in both weathered and unweathered tailings. After one year, plants grew better in amendments containing ashes in the field, also in those plants the metal and As shoot concentrations were generally lower than in other treatments. After two years, the only surviving plants were found in sewage sludge mixed with ashes. No effect on pH by plants was found in weathered acidic mine tailings in either field- or greenhouse experiment.     

Persistence of polycyclic aromatic hydrocarbons (PAHs) in sewage sludge-amended soil

The application of sewage sludge as a fertilizer is a common method used to improve soil properties. However, sewage sludge may contain various organic pollutants including polycyclic aromatic hydrocarbons. In the present study, the persistence of PAHs in soils fertilized with different sewage sludge doses was compared in relation to the sewage sludge dose applied (30, 75, 150, 300 and 600 Mgha(-1)) and the content of the polycyclic aromatic hydrocarbons in them. The experiment was carried out in two blocks of experimental plots divided according to the type of plants grown: field plants and perennial-willow. Sewage sludge addition to soils resulted in an increase in the content of polycyclic aromatic hydrocarbons in these soils. This increase was proportional to the quantity of sewage sludge applied. The results obtained showed that during a 42/54-month period, more than half of the individual PAHs introduced into the soil with sewage sludge were degraded. The scope of dissipation depended on the sewage sludge dose and the use to which the area was put. In the experiment with the willow only in the case of the highest sludge dose was a decrease in the PAH content above 50% noted; whereas in the case of the experiment with the field plants, it was higher by 50% for all sewage sludge doses. In experiment with field plants the highest scope of individual PAH disappearance was observed in the soil with the sewage sludge dose amounting to 300 Mgha(-1). In experiment with willow a relatively high dissipation of individual PAHs (>50%) was found in the treatment with the highest sludge dose (600 Mgha(-1)). A wider PAH dissipation range in the experiment with field plants was conditioned by the more favourable conditions created as a result of the breeding treatments applied. Agrotechnical treatments clearly increased the disappearance of the PAHs in those soils fertilized with the lowest sewage sludge doses (30 and 75 Mgha(-1)). The results obtained showed that the preferred method of treating a light soil fertilised with sewage sludges should be a one-year system, with a sludge application of 75 Mgha(-1).     

Organic Contaminants from Sewage Sludge Applied to Agricultural Soils. False Alarm Regarding Possible Problems for Food Safety? (8 pp)

Goal, Scope and Background Sewage sludge produced in wastewater treatment contains large amounts of organic matter and nutrients and could, therefore, be suitable as fertiliser. However, with the sludge, besides heavy metals and pathogenic bacteria, a variety of organic contaminants can be added to agricultural fields. Whether the organic contaminants from the sludge can have adverse effects on human health and wildlife if these compounds enter the food chain or groundwater still remains a point of controversial discussion. Main Features This paper presents an overview on the present situation in Europe and a summary of some recent results on the possible uptake of organic contaminants by crops after addition to agricultural fields by sewage sludge. Results Greenhouse experiments and field trials were performed to study the degradation and uptake of organic micro-contaminants in sludge-amended agricultural soil in crops, such as barley and carrots grown in agricultural soil amended with anaerobically-treated sewage sludge from a wastewater treatment plant, but studies hitherto have revealed no immediate risks. Common sludge contaminants such as linear alkylbenzene sulphonates (LAS), nonylphenol ethoxylates (NPE), polycyclic aromatic hydrocarbons (PAH), bis(diethylhexyl) phthalate (DEHP), showed neither accumulation in soil nor uptake in plants. Discussion It is assumed that the annual amount of sewage sludge produced in Europe will increase in the future, mainly due to larger amounts of high quality drinking water needed by an increasing population and due to increasing demands for cleaner sewage water. Application of sewage sludge to agricultural soils is sustainable and economical due to nutrient cycling and disposal of sewage sludge. However, this solution also involves risks with respect to the occurrence of organic contaminants and other potentially harmful contents such as pathogens and heavy metals present in the sludge. There have been concerns that organic contaminants may accumulate in the soil, be taken up by plants and thereby transferred to humans via the food chain. Results obtained so far revealed, however, no immediate risk of accumulation of common organic sludge contaminants in soil or uptake in plants when applying sewage sludge to agricultural soil. With very high dosages of sewage sludge, there may be a risk for accumulation of very apolar contaminants, such as DEHP, to the soil. Conclusions Any conclusions on the safe use of sewage sludge in agriculture have to be drawn carefully, as the studies performed until now have been limited. Further studies are required, and before final statements can be drawn, it is imminent to study a larger variety of common crops and the effect sewage sludge application may have on a possible accumulation of organic contaminants in the crops. Furthermore, a larger variety of organic contaminants need to be studied and special focus should be given to contaminants newly introduced into the environment. Besides investigating possible plant uptake of organic contaminants, the fate of these compounds in soil after sludge application need to be monitored too. Here, special attention has to begiven to studies on degradation and the formation of degradation products, to weathering and to leaching effects on groundwater, to the application of different crops on the same field (crop rotation), to the use of full-width tillage and strip tillage, and to long term application of sewage sludge on the soil. Recommendations and Perspectives There are environmental, political as well as economical incentives to increase the agricultural application of sludge. However, such usage should be performed with care as there are also ways in which sludge fertilisation could harm the environment and human health. Recently, a new European COST Action (859) has been established covering the field of food safety and improved food quality. Part of the Action is dealing with the application of sewage sludge in agriculture. Before any political and economical measures can be taken, the pros and cons have to be sufficiently investigated on a scientific level first. ESS-Submission Editor: Prof. Elena Maestri (elena.maestri@unipr.it)     

The uptake of cadmium and zinc by the bird-cherry oat aphid Rhopalosiphum padi (Homoptera:Aphididae) feeding on wheat grown on sewage sludge amended agricultural soil

A greenhouse trial investigated the uptake of cadmium and zinc by the bird-cherry oat aphid (Rhopalosiphum padi) feeding on wheat grown on sewage sludge amended soil. The trial was conducted at application rates of 0, 5, 7.5, 10, 15 and 20 tonnes ha(-1) dry solids. Concentrations of Cd and Zn were within current UK limits for potentially toxic elements in soils amended with sewage sludge. Cd and Zn in wheat plants were significantly greater than controls. Batches of aphids feeding on the wheat also showed a significant increase in the uptake of Cd and Zn. This study demonstrates a potential route of exposure to Cd and Zn for the predators of cereal aphids.     

Modelling phytoremediation by the hyperaccumulating fern, Pteris vittata, of soils historically contaminated with arsenic

Pteris vittata plants were grown on twenty-one UK soils contaminated with arsenic (As) from a wide range of natural and anthropogenic sources. Arsenic concentration was measured in fern fronds, soil and soil pore water collected with Rhizon samplers. Isotopically exchangeable soil arsenate was determined by equilibration with ⁷³As^V. Removal of As from the 21 soils by three sequential crops of P. vittata ranged between 0.1 and 13% of total soil As. Ferns grown on a soil subjected to long-term sewage sludge application showed reduced uptake of As because of high available phosphate concentrations. A combined solubility-uptake model was parameterised to enable prediction of phytoremediation success from estimates of soil As, ‘As-lability’ and soil pH. The model was used to demonstrate the remediation potential of P. vittata under different soil conditions and with contrasting assumptions regarding re-supply of the labile As pool from unavailable forms.     

Phosphorus flame retardants: properties, production, environmental occurrence, toxicity and analysis

Since the ban on some brominated flame retardants (BFRs), phosphorus flame retardants (PFRs), which were responsible for 20% of the flame retardant (FR) consumption in 2006 in Europe, are often proposed as alternatives for BFRs. PFRs can be divided in three main groups, inorganic, organic and halogen containing PFRs. Most of the PFRs have a mechanism of action in the solid phase of burning materials (char formation), but some may also be active in the gas phase. Some PFRs are reactive FRs, which means they are chemically bound to a polymer, whereas others are additive and mixed into the polymer. The focus of this report is limited to the PFRs mentioned in the literature as potential substitutes for BFRs. The physico-chemical properties, applications and production volumes of PFRs are given. Non-halogenated PFRs are often used as plasticisers as well. Limited information is available on the occurrence of PFRs in the environment. For triphenyl phosphate (TPhP), tricresylphosphate (TCP), tris(2-chloroethyl)phosphate (TCEP), tris(chloropropyl)phosphate (TCPP), tris(1,3-dichloro-2-propyl)phosphate (TDCPP), and tetrekis(2-chlorethyl)dichloroisopentyldiphosphate (V6) a number of studies have been performed on their occurrence in air, water and sediment, but limited data were found on their occurrence in biota. Concentrations found for these PFRs in air were up to 47 μg m(-3), in sediment levels up to 24 mg kg(-1) were found, and in surface water concentrations up to 379 ng L(-1). In all these matrices TCPP was dominant. Concentrations found in dust were up to 67 mg kg(-1), with TDCPP being the dominant PFR. PFR concentrations reported were often higher than polybrominated diphenylether (PBDE) concentrations, and the human exposure due to PFR concentrations in indoor air appears to be higher than exposure due to PBDE concentrations in indoor air. Only the Cl-containing PFRs are carcinogenic. Other negative human health effects were found for Cl-containing PFRs as well as for TCP, which suggest that those PFRs would not be suitable alternatives for BFRs. TPhP, diphenylcresylphosphate (DCP) and TCP would not be suitable alternatives either, because they are considered to be toxic to (aquatic) organisms. Diethylphosphinic acid is, just like TCEP, considered to be very persistent. From an environmental perspective, resorcinol-bis(diphenylphosphate) (RDP), bisphenol-A diphenyl phosphate (BADP) and melamine polyphosphate, may be suitable good substitutes for BFRs. Information on PFR analysis in air, water and sediment is limited to TCEP, TCPP, TPhP, TCP and some other organophosphate esters. For air sampling passive samplers have been used as well as solid phase extraction (SPE) membranes, SPE cartridges, and solid phase micro-extraction (SPME). For extraction of PFRs from water SPE is recommended, because this method gives good recoveries (67-105%) and acceptable relative standard deviations (RSDs) (<20%), and offers the option of on-line coupling with a detection system. For the extraction of PFRs from sediment microwave-assisted extraction (MAE) is recommended. The recoveries (78-105%) and RSDs (3-8%) are good and the method is faster and requires less solvent compared to other methods. For the final instrumental analysis of PFRs, gas chromatography-flame photometric detection (GC-FPD), GC-nitrogen-phosphorus detection (NPD), GC-atomic emission detection (AED), GC-mass spectrometry (MS) as well as liquid chromatography (LC)-MS/MS and GC-Inductively-coupled plasma-MS (ICP-MS) are used. GC-ICP-MS is a promising method, because it provides much less complex chromatograms while offering the same recoveries and limits of detection (LOD) (instrumental LOD is 5-10 ng mL(-1)) compared to GC-NPD and GC-MS, which are frequently used methods for PFR analysis. GC-MS offers a higher selectivity than GC-NPD and the possibility of using isotopically labeled compounds for quantification.     

Uptake of dioxin-like compounds from sewage sludge into various plant species--assessment of levels using a sensitive bioassay

A bioassay for the detection of dioxin-like compounds was used to estimate uptake of dioxin-like compounds in carrots, oil seed rape seeds, zucchinis and cucumbers grown in soil amended with sewage sludge from Swedish sewage treatment plants (STP). This sensitive bioassay is based on 7-ethoxyresorufin O-deethylase (EROD)-induction in cultured chicken embryo livers and reflects the combined biological effect of all dioxin-like compounds in a sample, including ones that seldom are analyzed. The bioassay detected low concentrations of dioxin-like compounds in all carrot, zucchini and cucumber samples, but did not detect any dioxin-like compounds in the rape seeds. In carrots the concentrations were increased up to seven times when grown in soil amended with high applications of some of the sludge samples, while others did not increase the concentrations compared to control. More realistic sludge applications only increased the concentrations slightly. The sludge-fertilized carrots contained the highest concentrations of the investigated plants (up to 14 pg bioassay-derived TCDD equivalents (bio-TEQs)/g d.w.). In the carrots, differences in uptake of dioxin-like compounds depended on the sludge origin, which may be due to more easily bioaccumulated dioxin-like compounds in some sludge samples, or other components that facilitated uptake into the carrots. In the cucumbers, a more than two-fold increase (from 0.2 to 0.5 pg bio-TEQs/g d.w.) was observed in specimens grown in sludge-amended soil when compared to controls, suggesting a small uptake from the roots to the shoots. No sludge-dependent increase in uptake was seen in the zucchini fruits. The bio-TEQ levels were generally low in the consumable above ground plant parts of the investigated species. However, the question if repeated sludge application results in a soil accumulation of dioxin-like compounds, thereby increasing the risk of plant uptake, remains to be investigated.     

Bioaccumulation and the soil factors affecting the uptake of arsenic in earthworm, Eisenia fetida

To better understand arsenic (As) bioaccumulation, a soil invertebrate species was exposed to 17 field soils contaminated with arsenic due to mining activity. Earthworms (Eisenia fetida) were kept in the soils for 70 days under laboratory conditions, as body burden increased and failed to reach equilibrium in all soils. After 70 days of exposure, XANES spectra determined that As was biotransformed to a highly reduced form. Uptake kinetics for As was calculated using one compartment model. Stepwise multiple regression suggested that sorbed As in soils are bioaccessible, and uptake is governed by soil properties (iron oxide, sulfate, and dissolved organic carbon) that control As mobility in soils. As in soil solution are highly related to uptake rate except four soils which had relatively high chloride or phosphate. The results imply that uptake of As is through As interaction with soil characteristics as well as direct from the soil solution. Internal validation showed that empirically derived regression equations can be used for predicting As uptake as a function of soil properties within the range of soil properties in the data set.     

Biological and ecophysiological reactions of white wall rocket (Diplotaxis erucoides L.) grown on sewage sludge compost

We studied the effects of sewage sludge compost on white wall rocket (Diplotaxis erucoides L.) compared with mineral fertilization and control (without any fertilizer) in a greenhouse experiment. The plants grown on the compost-amended soil showed a different growth dynamic: a significant delay in flowering and a bigger root system. Both the compost and the fertilization treatments increased biomass and seed yield. Heavy metal (Cu, Cd, Zn, Ni) distribution within the plant was in the following order: roots > leaves > stems, except for zinc which was homogeneously distributed. The balance of mineral nutrition was not affected by treatments. Zinc was the trace element which was most taken up. Unlike many species of Brassicaceae, white wall rocket is not a hyperaccumulator. Although sewage sludge compost improved plant growth, delay in flowering shows that it is necessary to take precautions when spreading sewage sludge in natural areas.     

Effects of sewage sludge amendment on heavy metal accumulation and consequent responses of Beta vulgaris plants

Use of sewage sludge, a biological residue produced from sewage treatment processes in agriculture is an alternative disposal technique of waste. To study the usefulness of sewage sludge amendment for palak (Beta vulgaris var. Allgreen H-1), a leafy vegetable and consequent heavy metal contamination, a pot experiment was conducted by mixing sewage sludge at 20% and 40% (w/w) amendment ratios to the agricultural soil. Soil pH decreased whereas electrical conductance, organic carbon, total N, available P and exchangeable Na, K and Ca increased in soil amended with sewage sludge in comparison to unamended soil. Sewage sludge amendment led to significant increase in Pb, Cr, Cd, Cu, Zn and Ni concentrations of soil. Cd concentration in soil was found above the Indian permissible limit in soil at both the amendment ratios.

The increased concentration of heavy metals in soil due to sewage sludge amendment led to increases in heavy metal uptake and shoot and root concentrations of Ni, Cd, Cu, Cr, Pb and Zn in plants as compared to those grown on unamended soil. Accumulation was more in roots than shoots for most of the heavy metals. Concentrations of Cd, Ni and Zn were more than the permissible limits of Indian standard in the edible portion of palak grown on different sewage sludge amendments ratios. Sewage sludge amendment in soil decreased root length, leaf area and root biomass of palak at both the amendment ratios, whereas shoot biomass and yield decreased significantly at 40% sludge amendment. Rate of photosynthesis, stomatal conductance and chlorophyll content decreased whereas lipid peroxidation, peroxidase activity and protein and proline contents, increased in plants grown in sewage sludge-amended soil as compared to those grown in unamended soil.

The study clearly shows that increase in heavy metal concentration in foliage of plants grown in sewage sludge-amended soil caused unfavorable changes in physiological and biochemical characteristics of plants leading to reductions in morphological characteristics, biomass accumulation and yield. The study concludes that sewage sludge amendment in soil for growing palak may not be a good option due to risk of contamination of Cd, Ni and Zn and also due to lowering of yield at higher mixing ratio.     

The effects of different sewage sludge amendment rates on the heavy metal bioaccumulation,growth and biomass of cucumbers (Cucumis sativus L.)

When sewage sludge is incorrectly applied, it may adversely impact agro-system productivity. Thus, this study addresses the reaction of Cucumis sativus L. (cucumber) to different amendment rates (0, 10, 20, 30, 40 and 50 g kg^?1) of sewage sludge in a greenhouse pot experiment, in which the plant growth, heavy metal uptake and biomass were evaluated. A randomized complete block design with six treatments and six replications was used as the experimental design. The soil electrical conductivity, organic matter and Cr, Fe, Zn and Ni concentrations increased, but the soil pH decreased in response to the sewage sludge applications. As approved by the Council of European Communities, all of the heavy metal concentrations in the sewage sludge were less than the permitted limit for applying sewage sludge to land. Generally, applications of sewage sludge of up to 40 g kg^?1 resulted in a considerable increase in all of the morphometric parameters and biomass of cucumbers in contrast to plants grown on the control soil. Nevertheless, the cucumber shoot height; root length; number of leaves, internodes and fruits; leaf area; absolute growth rate and biomass decreased in response to 50 g kg^?1 of sewage sludge. All of the heavy metal concentrations (except the Cu, Zn and Ni in the roots, Mn in the fruits and Pb in the stems) in different cucumber tissues increased with increasing sewage sludge application rates. However, all of the heavy metal concentrations (except the Cr and Fe in the roots, Fe in the leaves and Cu in the fruits) were within the normal range and did not reach phytotoxic levels. A characteristic of these cucumbers was that all of the heavy metals had a bioaccumulation factor <1.0. All of the heavy metals (except Cd, Cu and Zn) had translocation factors that were <1.0. As a result, the sewage sludge used in this study could be considered for use as a fertilizer in cucumber production systems in Saudi Arabia and can also serve as a substitute method of sewage sludge disposal.

The effects of different sewage sludge amendment rates on the heavy metal bioaccumulation, growth and biomass of cucumbers

     

Measuring emissions of organophosphate flame retardants using a passive flux sampler

Flame retardants are used in polymers to reduce the flammability of building materials, electric appliances, fabric and papers. In recent years, organophosphate flame retardants have been used as substitutes for polybrominated flame retardants (BFRs). In Japan, the amount of organophosphate flame retardants used in 2001 was about five times more than in 2000. Recently, several studies have shown the health concerns for some organophosphate flame retardants. Little research has been performed on the emission of organophosphate flame retardants, especially the relationship between content and emissions. In this study, a new type of passive sampler was developed to measure emissions of organophosphate flame retardants from plastic materials. With this sampler, emissions from polyvinyl chloride wallpaper samples with different content of tris(2-chloroisopropyl)phosphate (TCPP) at different temperatures were examined. The observed maximum emissions of TCPP from 1, 3, 5, 10 and 20 w/w% content wallpaper materials were 262.3, 452.6, 644.8, 1119.1 and 2166.8 μg m⁻² h⁻¹, respectively. Emissions from 5% TCPP content materials at 40 and 60 °C were 1135.7 and 2841.2 μg m⁻² h⁻¹, respectively. A significantly positive correlation between the flux of TCPP and the TCPP content of the wallpaper samples was observed. A linear relationship was found between the inverse of temperature and the logarithm of TCPP emission. The results imply that the use of materials with a high organophosphate flame retardant content can lead to high emission rates in high-temperature indoor environments.     

The role of dissolved organic carbon in the mobility of Cd, Ni and Zn in sewage sludge-amended soils

A pot experiment was conducted to investigate the effect of application of naturally derived dissolved organic compounds (DOC) on the uptake of Cd, Ni and Zn by Lolium perenne L. from mixtures of soil and sewage sludge and on their extractability with CaCl2. DOC was applied at concentrations of 0, 285 and 470 mg l(-1) to a loamy sand (LS) and a sandy clay loam (SCL) soil mixed with sewage sludge at rates equivalent to 0, 10 and 50 t ha(-1). DOC applications significantly increased the extractability of metals and also their uptake by ryegrass, but the increase was greater where sludge was applied at 50 t ha(-1). It is suggested that DOC in soils significantly increased the availability of the metals to plants. This was especially the case in the LS soil, where DOC had less competition with surface sorption than in the SCL soil.     

Uptake and translocation of metformin, ciprofloxacin and narasin in forage- and crop plants

Transfer of bioactive organic compounds from soil to plants might represent animal and human health risks. Sewage sludge and manure are potential sources for bioactive compounds such as human- and veterinary drugs. In the present study, uptake of the anti-diabetic compound, metformin, the antibiotic agent ciprofloxacin and the anti-coccidial narasin in carrot (Daucuscarota ssp. sativus cvs. Napoli) and barley (Hordeumvulgare) were investigated. The pharmaceuticals were selected in order to cover various chemical properties, in addition to their presence in relevant environmental matrixes. The root concentration factors (RCF) found in the present study were higher than the corresponding leaf concentration factors (LCF) for the three test pharmaceuticals. The uptake of metformin was higher compared with ciprofloxacin and narasin for all plant compartments analyzed. Metformin was studied more explicitly with regard to uptake and translocation in meadow fescue (Festucapratense), three other carrot cultivars (D.carota ssp. sativus cvs. Amager, Rothild and Nutri Red), wheat cereal (Triticumaestivum) and turnip rape seed (Brassicacampestris). Uptake of metformin in meadow fescue was comparable with uptake in the four carrot cultivars (RCF 2-10, LCF approximately 1.5), uptake in wheat cereals were comparable with barley cereals (seed concentration factors, SCF, 0.02-0.04) while the accumulation in turnip rape seeds was as high as 1.5. All three pharmaceuticals produced negative effects on growth and development of carrots when grown in soil concentration of 6-10 mg kg⁻¹ dry weight.     

Determination of selected pharmaceuticals and caffeine in sewage and seawater from Tromsø/Norway with emphasis on ibuprofen and its metabolites

Selected pharmaceuticals, among them analgesics, ss-blockers and anti-depressants as well as caffeine, the anti-bacterial triclosan and the insect repellent N,N-diethyl-3-toluamide (DEET) were determined in different sewage samples (sewage treatment plants, hospital effluents) from Troms?/Norway and in seawater from Troms?-Sound, into which the sewage is discharged. While caffeine, triclosan, ibuprofen and its major metabolites hydroxy- and carboxy-ibuprofen were present in all sewage samples, additional pharmaceuticals were observed in sewage containing hospital effluents. Concentrations were in the range of 20-293 microg/l (caffeine), 0.2-2.4 microg/l (triclosan) and 0.1-20 microg/l (sum ibuprofen + metabolites). In seawater, only caffeine (7-87 ng/l), DEET (0.4-13 ng/l) and ibuprofen + metabolites (sum concentration < LOQ-7.7 ng/l) were detected. Ibuprofen and its metabolites hydroxy- and carboxy-ibuprofen were quantified individually by use of the respective reference compounds. Relative amounts of the three compounds were determined in different types of water showing characteristic patterns, with hydroxy-ibuprofen being the major component in sewage whereas carboxy-ibuprofen was dominant in seawater samples. The patterns which were compared to those observed in similar samples from Germany indicated different transformation behaviour under limnic and marine conditions.     

Effects of short-term pH fluctuations on cadmium, nickel, lead, and zinc availability to ryegrass in a sewage sludge-amended field

In this field experiment, sewage sludge was applied at 0, 5, 10, and 50tha(-1), and the availability of Cd, Ni, Pb, and Zn was assessed both by ryegrass uptake and by DTPA extractions. The aim was to investigate the role of important soil parameters, particularly pH, on heavy metal availability. It was found that metal uptake and extractability increased significantly in the 50tha(-1) treatment. In the 16th week of the experiment there was a significant, although temporary, increase in DTPA-extractable Cd, Ni, and Zn concentrations. Metal concentrations in ryegrass were also significantly elevated in week 20 compared to the subsequent cuttings. These fluctuations in both DTPA and ryegrass uptake occurred only at 50tha(-1) and were probably induced by a sudden pH decrease measured in the same treatment in week 16. This suggests that soils which have received high applications of sewage sludge may be prone to fluctuations in metal availability.     

Bioavailability and plant accumulation of heavy metals and phosphorus in agricultural soils amended by long-term application of sewage sludge

Amendment of agricultural soils with municipal sewage sludges provides a valuable source of plant nutrients and organic matter. Nevertheless, addition of heavy metals and risks of eutrophication continue to be of concern. Metal behaviour in soils and plant uptake are dependent on the nature of the metal, sludge/soil physico-chemical properties and plant species. A pot experiment was carried out to evaluate plant production and heavy metal uptake, soil heavy metal pools and bioavailability, and soil P pools and possible leaching losses, in agricultural soils amended with sewage sludge for at least 10 years (F20) compared to non-amended soils (control). Sewage sludge application increased soil pH, N, Olsen-extractable-P, DOC and exchangeable Ca, Mg and K concentrations. Total and EDTA-extractable soil concentrations of Cu and Zn were also significantly greater in F20, and soil metal (Cu, Mn and Zn) and P fractionation altered. Compared to the control, in F20 relative amounts of acid-extractable (Mn, Zn), reducible (Mn, Zn) and oxidisable (Cu, Zn) metal fractions were greater, and a dominance of inorganic P forms was observed. Analyses of F20 soil solutions highlighted risks of PO4 and Cu leaching. However, despite the observed increases in metal bioavailability sewage sludge applications did not lead to an increase in plant shoot concentrations (in wild plants or crop species). On the contrary, depending on the plant species, Mn and Zn tissue concentrations were within the deficiency level for most plants.     

Model evaluation of the phytoextraction potential of heavy metal hyperaccumulators and non-hyperaccumulators

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.