After entry into force of the Stockholm Convention and Aarhus Protocol and in order to implement the upcoming European legal background, the European countries are asked to apply control measures to reduce the release of persistent organic pollutants (POPs) such as dioxins and furans (PCDD/PCDF) and polychlorinated biphenyls as well as to establish POPs release inventories. In this perspective, development of measuring techniques of emissions is a focal issue in acquiring useful information. In this paper, results of various measurement campaigns at different municipal waste incineration (MWI) plants using long-term automated sampling of PCDD/PCDF are presented. The samples collected from both manual and automated campaigns were analyzed following the European Standard EN-1948:2006 by high-resolution gas chromatograph/high-resolution mass spectrometer. Performances of two different commercial systems have been investigated. Anomalous values occurred during one long-term campaign (22.16 pg I-toxic equivalent (TEQ)/Nm3), compared to average values (4–5 pg I-TEQ/Nm3) of the MWI. At this maximum value, a main occurrence of abnormal and instable operating conditions has been found. Sampling based on long-term basis was found to be more reliable to monitor PCDD/PCDF emissions than occasional short-term sampling. Nevertheless, the results of long-term campaigns demonstrate that emission levels detected in 15–30 days campaigns, when unsteady operating conditions can occur, as start-up and shut down, are not immediately comparable to the typical levels in a 6–8 h, when operating conditions are generally stable. Moreover, there are often differences observed in the congener profiles between short- and long-term campaigns.

GOAL, SCOPE, AND BACKGROUND: Many studies have focused on measuring fine and course particulate matter (PM) in urban and rural sites around the world. The aim of this research is to gain information on the size distribution of particles. The physical characteristics of PM in the urban air of Istanbul were determined. METHODS: PM sampling was carried out at five stations (Avcılar, Beşiktaş, Kilyos, Rasathane, and Göztepe) over a period of 2 years. PM filter samples were collected for eight different size ranges (<0.43, 0.43–1, 1–1.7, 1.7–2.6, 2.6–3.5, 3.5–5.2, 5.2–6.5, 6.5–8, and >8 μm) using a Cascade Impactor. The size distributions of the PM samples were determined. RESULTS AND DISCUSSION: The mean total PM concentrations were 48.6 ± 34.0, 34.8 ± 11.6, 28.6 ± 13.6, 21.5 ± 9.1, and 16.8 ± 5.1 μg/m3 for the Göztepe, Beşiktaş, Avcılar, Rasathane, and Kilyos stations, respectively. The total PM concentrations were found to be 1.2–1.5 times higher in the fall and winter than in the spring and summer, except for at the station in Avcılar. The PM concentrations in Avcılar did not exhibit seasonal variations. This is thought to result from the intense industrial activity in the area. PM2.6 (below 2.6 μm particles) comprised up to 62% of the total amount of PM in samples collected at the Göztepe, Beşiktaş, and Rasathane stations during the fall and winter. PM1 was determined to be approximately 45% of the total, corresponding to 57% of the amount of PM2.5. A multi-modal PM size distribution was observed. The lowest Mass Median Aerodynamic Diameter (MMAD) values observed in Avcılar, Beşiktaş, Rasathane, and Göztepe were 4.2, 3.9, 2.9, and 3.5 μm, respectively, and were observed during the season of active household heating. No difference was measured in the MMAD values (5.2 μm) between the seasons of heating and non-heating in Kilyos.

INTRODUCTION: Environmental safe and friendly management and disposal of wastewater sludge is a problem of every treatment plant throughout the world. Bioseparation and dewaterability of raw domestic wastewater sludge were evaluated for proper management and disposal by mycoremediation, i.e., using prior grown 2% (v/v) spore suspension of filamentous fungal (Mucor hiemalis Wehmer) broth inoculation, which were grown in 2% (w/v) solution of malt extract and wheat flour for 48–60 h in orbital shaker. DISCUSSION: Within 2–3 days of treatment application, encouraging results were achieved in total dry solids (TDS), total suspended solid (TSS), turbidity, chemical oxygen demand (COD), specific resistance to filtration (SRF), and pH due to fungal treatment in recognition of bioseparation and dewaterability of wastewater sludge compared to control. The significant reduction of TDS was remarked at fungal biomass (FB) in wheat flour (WF) treatment. The removal of TSS, turbidity, COD, and SRF were observed 96.0%, 99.4%, 92.6%, and 97.6%, respectively, in supernatant at 5 days by FB in WF. The SRF measuring the dewaterability was decreased with maximum (0.26 × 10−12 mg/kg) equivalent to 95.5% at 2 days in FB in WF also. FB in WF broth is a potential, environmental friendly, comparatively low-cost biological technique which might play the significant role for bioremediation and bioseparation of domestic wastewater sludge. The present technique may bring a dynamic change in treatment of wastewater in future.

PURPOSE: Due to the fast development of industry and the overuse of agrichemicals in past decades, Lake Taihu, an important source of aquatic products for Eastern China, has simultaneously suffered mercury (Hg) contamination and eutrophication. The objectives of this study are to understand Hg transfer in the food web in this eutrophic, shallow lake and to evaluate the exposure risk of Hg through fish consumption. METHODS: Biota samples including macrophytes, sestons, benthic animals, and fish were collected from Lake Taihu in the fall of 2009. The total mercury (THg), methyl mercury (MeHg), δ¹³C and δ¹⁵N in the samples were measured. RESULTS AND DISCUSSION: The signature for δ¹⁵N increased with the trophic levels. Along with a diet composed of fish, the significant relationship between the δ¹³C and δ¹⁵N indicated that a pelagic foraging habitat is the dominant pathway for energy transfer in Lake Taihu. The concentrations of THg and MeHg in the organisms varied dramatically by ∼3 orders of magnitude from primary producers (macrophytes and sestons) to piscivorous fish. The highest concentrations of both THg (100 ng g⁻¹) and MeHg (66 ng g⁻¹), however, were lower than the guideline of 200 ng g⁻¹ of MeHg for vulnerable populations that is recommended by the World Health Organization (WHO). The daily intake of THg and MeHg of 92 and 56 ng day⁻¹ kg⁻¹ body weight, respectively, was generally lower than the tolerable intake of 230 ng day⁻¹ kg⁻¹ body weight for children recommended by the Joint FAO/WHO Expert Committee on Food Additives. Significant relationships between the δ¹⁵N and the logarithm of THg and MeHg showed an obvious biomagnification of Hg along the food web. The logarithmic bioaccumulation factor of MeHg in the fish (up to 5.7) from Lake Taihu, however, was relatively low compared to that of other aquatic ecosystems. CONCLUSION: Health risk of exposure to Hg by consumption of fish for local residents is relatively low in the Lake Taihu area. Dilution of Hg levels in the phytoplankton induced by eutrophication is a possible factor inhibiting accumulation of MeHg in fish in eutrophic Lake Taihu.

According to the European legislation, REACH, organic compounds are considered as substances of very high concern (SVHC) if they are persistent, bioaccumulative and toxic (PBT). A substance’s long-range transport potential (LRTP) may also pose a risk to remote regions. This is, however, not yet explicitly included. For identification of compounds, which are not PBT according to REACH criteria, but show LRTP, we investigated 22,438 compounds from the Canadian Domestic Substance List (CDSL). The CDSL was searched for organic, neutral compounds. Substance properties were estimated with EPI Suite v4.00. Next, the substance list was edited in two ways: (1) The half-life criterion in air for LRTP as defined in the Stockholm Convention was applied. (2) For all compounds, indicators for persistence and LRTP were calculated with the multimedia model ELPOS v2.2. Applying the half-life criterion, we identified 594 substances, which are prone to LRT but are not PBT (non-PBT-L substances). In contrast, investigations with ELPOS lead to a shorter list of 188 substances, which are non-PBT-L substances. Finally, the list was compared with potential Arctic contaminants identified in previous literature. Our results show that there is a large number of organic chemicals which would not be considered as SVHC since they are not, at the same time, persistent, bioaccumulative and toxic according to REACH criteria. Nevertheless, they show LRTP according to different screening approaches and thus a potential hazard to remote regions.

The objectives of the present study were to compare nine dominant plant species growing in mine tailings and nonmining areas in terms of biomass and Cd concentrations and to search for Cd accumulation and tolerance. Also, more detailed experiments were conducted on Athyrium wardii using a pot experiment to assure its Cd-accumulation ability and tolerance as a potential phytostabilizer of Cd-polluted soils. Nine dominant plant species growing on Pb/Zn mine tailings and their corresponding nonmining ecotypes were investigated for their potential to phytostabilize Cd. The performance of A. wardii exposed to high levels of Cd was investigated under controlled conditions. A field study revealed that the Cd concentrations in the roots of these plants ranged from 0.21 to 251.07 mg kg−1, and the highest concentrations were found in A. wardii, which reached a concentration of 69.78, 251.07, and 126.35 mg kg−1 during the early growth stage (May), vigorous growth stage (August), and late growth stage (October), respectively. The Cd concentrations of roots among the nine mining ecotypes were positively correlated with available content of Cd in the rhizosphere soils, whereas a negative correlation was observed in the nonmining ecotypes. A pot experiment showed that the mining ecotype of A. wardii had a higher biomass production and Cd retention capacity in roots than that of the nonmining ecotype. Due to the relatively high tolerance to Cd and the capacity of roots to retain this metal, A. wardii may be useful for the phytostabilization of soils contaminated by Cd.

PURPOSE: The objective of this paper is to assess the regulation of the accumulation of heavy metals in the aquatic environment and different fish species. METHODS: Water and fish samples were collected from upper to lower reaches of the Yangtze River. The heavy metal (Cd, Cr, Cu, Hg, Pb, Zn) concentrations in the muscle tissue of seven fishes were measured. Additionally, the relationships between heavy metal concentrations in fish tissue and fish size (length and weight), condition factor, water layer distribution, and trophic level were investigated. RESULTS: Metal concentrations (milligrams per kilogram wet weight) were found to be distributed differently among different fish species. The highest concentrations of Cu (1.22 mg/kg) and Zn (7.55 mg/kg) were measured in Pelteobagrus fulvidraco, the highest concentrations of Cd (0.115 mg/kg) and Hg (0.0304 mg/kg) were measured in Silurus asotus, and the highest concentrations of Pb (0.811 mg/kg) and Cr (0.239 mg/kg) were measured in Carassius auratus and Cyprinus carpio. A positive relationship was found between fish size and metal level in most cases. The variance of the relationships may be the result of differences in habitat, swimming behavior, and metabolic activity. In this study, fishes living in the lower water layer and river bottom had higher metals concentrations than in upper and middle layers. Benthic carnivorous and euryphagous fish had higher metals concentrations than phytoplankton and herbivorous fish. Generally, fish caught from the lower reach had higher metals concentrations than those from the upper reach. CONCLUSIONS: Cadmium and lead concentrations in several fishes exceeded the permissible food consumption limits, this should be considered to be an important warning signal.

PURPOSE: Instrumental capabilities and software tools of modern hybrid mass spectrometry (MS) instruments such as high-resolution mass spectrometry (HRMS), quadrupole time-of-flight (QTOF), and quadrupole linear ion trap (QLIT) were experimentally investigated for the study of emerging contaminants in Henares River water samples. METHODS: Automated screening and confirmatory capabilities of QTOF working in full-scan MS and tandem MS (MS/MS) were explored when dealing with real samples. Investigations on the effect of sensitivity and resolution power influence on mass accuracy were studied for the correct assignment of the amoxicillin transformation product 5(R) amoxicillin-diketopiperazine-2′,5′ as an example of a nontarget compound. On the other hand, a comparison of quantitative and qualitative strategies based on direct injection analysis and off-line solid-phase extraction sample treatment were assayed using two different QLIT instruments for a selected group of emerging contaminants when operating in selected reaction monitoring (SRM) and information-dependent acquisition (IDA) modes. RESULTS AND DISCUSSION: Software-aided screening usually needs a further confirmatory step. Resolving power and MS/MS feature of QTOF showed to confirm/reject most findings in river water, although sensitivity-related limitations are usually found. Superior sensitivity of modern QLIT-MS/MS offered the possibility of direct injection analysis for proper quantitative study of a variety of contaminants, while it simultaneously reduced the matrix effect and increased the reliability of the results. Confirmation of ethylamphetamine, which lacks on a second SRM transition, was accomplished by using the IDA feature. CONCLUSION: Hybrid MS instruments equipped with high resolution and high sensitivity contributes to enlarge the scope of targeted analytes in river waters. However, in the tested instruments, there is a margin of improvement principally in required sensitivity and data treatment software tools devoted to reliable confirmation and improved automated data processing.

PURPOSE: A multiple inputs and multiple outputs (MIMO) fuzzy-logic-based model was proposed to estimate color and chemical oxygen demand (COD) removal efficiencies in the post-treatment of anaerobically pretreated poultry manure wastewater effluent using Fenton's oxidation process. Three main input variables including initial pH, Fe+2, and H2O2 dosages were fuzzified in a new numerical modeling scheme by the use of an artificial intelligence-based approach. MATERIALS AND METHODS: Trapezoidal membership functions with eight levels were conducted for the fuzzy subsets, and a Mamdani-type fuzzy inference system was used to implement a total of 70 rules in the IF–THEN format. The product (prod) and the center of gravity (centroid) methods were applied as the inference operator and defuzzification methods, respectively. Fuzzy-logic predicted results were compared with the outputs of two first-order polynomial regression models derived in the scope of this study. Estimated results were also compared to the multiple regression approach by means of various descriptive statistical indicators, such as root mean-squared error, index of agreement, fractional variance, proportion of systematic error, etc. RESULTS AND DISCUSSION: Results of the statistical analysis clearly revealed that, compared to conventional regression models, the proposed MIMO fuzzy-logic model produced very smaller deviations and demonstrated a superior predictive performance on forecasting of color and COD removal efficiencies with satisfactory determination coefficients over 0.98. CONCLUSIONS: Due to high capability of the fuzzy-logic methodology in capturing the non-linear interactions, it was demonstrated that a complex dynamic system, such as Fenton's oxidation, could be easily modeled.

PURPOSE: A former wood exploitation revealing high Cu and As concentration of the soils served as a case study for assisted phytoextraction. METHOD: P-spiked Linz–Donawitz (LD) slag was used as a soil additive to improve physico-chemical soil properties and in situ stabilize Cu and other trace metals in a sandy Cu-contaminated soil (630 mg kg−1 soil). The LD slag was incorporated into the contaminated soil to consist four treatments: 0% (T1), 1% (T2), 2% (T3), and 4% (T4). A similar uncontaminated soil was used as a control (CTRL). After a 1-month reaction period, potted soils were used for a 2-week growth experiment with dwarf beans. RESULTS: Soil pH increased with the incorporation rate of LD slag. Similarly the soil electrical conductivity (EC, in millisiemens per centimetre) is ameliorated. Bean plants grown on the untreated soil (T1) showed a high phytotoxicity. All incorporation rates of LD slag increased the root and shoot dry weight yields compared to the T1. The foliar Ca concentration of beans was enhanced for all LD slag-amended soil, while the foliar Mg, K, and P concentrations were not increased. Foliar Cu, Zn, and Cr concentrations of beans decreased with the LD slag incorporation rate. CONCLUSIONS: P-spiked LD slag incorporation into polluted soil allow the bean growth and foliar Ca concentration, but also to reduce foliar Cu concentration below its upper critical value avoiding an excessive soil EC and Zn deficiency. This dual effect can be of interest for soil remediation at larger scale.