Variability in microbial carbon isotope fractionation of tetra- and trichloroethene upon reductive dechlorination

The variability of stable carbon isotope fractionation upon reductive dechlorination of tetra- and trichloroethene by several microbial strains was investigated to examine the uncertainties related to the in situ application of compound specific isotope analysis (CSIA) of chlorinated ethenes. Carbon isotope fractionation was investigated with a set of microorganisms representative for the currently known diversity of dehalorespirers: Dehalococcoides ethenogenes strain 195, Desulfitobacterium sp. strain Viet1, Desulfuromonas michiganensis and Geobacter lovleyi sp. strain SZ and compared to the previous reports using Sulfurospirillum spp. and Desulfitobacterium sp. strain PCE-S. Carbon isotope fractionation of tetrachloroethene (PCE) and trichlorethene (TCE) was highly variable ranging from the absence of significant fractionation to carbon isotope fractionation (epsilonC) of 16.7 and 3.5-18.9 for PCE and TCE, respectively. Fractionation of both compounds by D. ethenogenes strain 195 (PCE: epsilonC=6.0; TCE: epsilonC=13.7) was similar to the literature data for mixed cultures containing Dehalococcoides spp. D. michiganensis (PCE: no significant fractionation; TCE: epsilonC=3.5) and G. lovleyi sp. strain SZ (PCE no significant fractionation; TCE: epsilonC=8.5) generated the lowest fractionation of all studied strains. Desulfitobacterium sp. strain Viet1 (PCE: epsilonC=16.7) gave the highest enrichment factor for PCE.     

Spatial trends of polyfluorinated compounds in guillemot (Uria aalge) eggs from North-Western Europe

Polyfluorinated alkyl compounds (PFCs) are a group of chemicals of growing concern that have been detected in biological and abiotic samples worldwide. This study reports the concentrations of a suite of PFCs: perfluorooctyl sulfonate (PFOS), perfluorooctyl sulfonamide (PFOSA) and perfluorinated carboxylic acids (PFCAs) in guillemot (Uria aalge) eggs, collected in North-Western Europe, from Iceland, the Faroe Islands, Sweden and two locations in Norway. The highest concentrations of PFOS were found in samples from Sweden (mean 400 ng g(-1) wet weight (w.w.)), which were almost five times higher than concentrations found in Norwegian samples (mean 85 ng g(-1)w.w. from both sample sites). The concentrations found in Icelandic and Faroe samples were lowest (mean 16 and 15 ng g(-1)w.w., respectively). Only Swedish samples differed significantly from the other locations. In general, PFCAs show a different spatial trend than PFOS. Perfluorooctanoic acid (PFOA) was not detected in any sample and perfluorononanoic acid (PFNA) was only detected in samples from Sweden. The most abundant PFCA was perfluoroundecanoic acid (PFUA) with highest concentrations in samples from Sweden (mean 82 ng g(-1)w.w.), samples from the Faroe Islands had the second highest concentration (mean 57 ng g(-1)w.w.) and samples from Iceland and Norway had concentrations ranging between 18 and 30 ng g(-1)w.w. The original hypothesis was based on the idea that PFC concentrations are the highest close to more densely populated and industrialized areas and lower levels in remote areas. However, the geographic pattern is more complicated than predicted and varies among different PFCs.     

Polycyclic aromatic hydrocarbon sampling in wastewaters using semipermeable membrane devices: accuracy of time-weighted average concentration estimations of truly dissolved compounds

Semipermeable membrane devices (SPMDs) previously spiked with performance reference compounds were exposed in wastewater. After 6 days of exposure, 13 polycyclic aromatic hydrocarbons (PAHs) were quantified in SPMDs. Exchange rate constants and time-weighted average (TWA) concentrations of SPMD-available PAHs in water were calculated. The bias of using SPMDs to estimate an actual TWA concentration if the concentration in water fluctuates, as can be expected in wastewater, was studied with numerical simulations. The bias increased with the exchange rate constant. However, most exchange rate constants evaluated in SPMDs exposed in wastewater were small enough for SPMDs to estimate a TWA concentration of PAHs even when the water concentration varied. TWA-SPMD-available concentrations were always below total dissolved (operationally defined as 0.7 microm) concentrations, indicating that part of the dissolved PAHs was not available for sampling. In situ partitioning coefficients K(DOC) were computed and found to be slightly higher than data from the literature. This confirms that only truly dissolved PAHs should be sampled by SPMDs in wastewater.     

X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by Fe-bearing minerals

The long-lived radionuclide ⁷⁹Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (Se^VIO₄²⁻) and selenite (Se^IVO₃²⁻). Previous investigations have demonstrated, however, that Se^IV and Se^VI are reduced by surface-associated Fe^II, thereby forming insoluble Se⁰ and Fe selenides. Here we show that the mixed Fe^II/^III (hydr)oxides green rust and magnetite, and the Fe^II sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the Fe^II carbonate siderite produces elemental Se. In the case of mackinawite, both S^−II and Fe^II surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these Fe^II systems is controlled by the concentration of HSe⁻; Se⁰ forms only at lower HSe⁻ concentrations related to slower HSeO₃⁻ reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe²⁺-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 × 10^− 8 M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since Fe^II phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product ⁷⁹Se may be much lower than previously assumed.     

Effect of sampling effort and sampling frequency on the composition of the planktonic crustacean assemblage: a case study of the river Danube

Although numerous studies have focused on the seasonal dynamics of riverine zooplankton, little is known about its short-term variation. In order to examine the effects of sampling frequency and sampling effort, microcrustacean samples were collected at daily intervals between 13 June and 21 July of 2007 in a parapotamal side arm of the river Danube, Hungary. Samples were also taken at biweekly intervals from November 2006 to May 2008. After presenting the community dynamics, the effect of sampling effort was evaluated with two different methods; the minimal sample size was also estimated. We introduced a single index (potential dynamic information loss; to determine the potential loss of information when sampling frequency is reduced. The formula was calculated for the total abundance, densities of the dominant taxa, adult/larva ratios of copepods and for two different diversity measures. Results suggest that abundances may experience notable fluctuations even within 1 week, as do diversities and adult/larva ratios.     

Total metal levels in crayfish Astacus leptodactylus (Eschscholtz, 1823), and surface sediments in Lake Terkos, Turkey

The aim of this study was to determine the total metal accumulation (aluminium, copper, manganese, lead, cadmium and iron) in different organs and eggs of Astacus leptodactylus (Eschscholtz, 1823) and sediments total metal contents (aluminium, copper, manganese, lead, cadmium, iron, zinc, chromium, nickel) in Lake Terkos. Water and sediment samples were collected from two stations at two different depths (1 and 2 m) of Lake Terkos in May 2008. Crayfish samples were collected by trammel net at the same region. Primary hydrographic conditions, such as temperature (13.6–19.4°C), salinity (0.27–0.34‰), dissolved oxygen (7.04–12.30 mg l^???1) and pH (7.42–8.51), were recorded for each sampling point. Moreover, the total organic carbon (1.65–5.44%) and the total calcium carbonate contents (19.44–41.16%) of sediment samples were determined. According to the Turkish Food Codex (J Zool 26:283–288, 2002), the maximum allowable Pb and Cd levels in crayfish are 0.5 mg/kg wet weight. Accordingly, the Pb and Cd levels determined in A. leptodactylus samples are below this limit. However, when compared with the acceptable metal limits defined by WHO, Australian National Health and Medical Research Council and Ministry of Agriculture in United Kingdom (UK), it is clear that the Cu level is at the limit and the Cd results exceed the limit. When the metal contents in sediment samples from Lake Terkos are examined, it is seen that the Al, Fe, Mn, Ni and Cu contents are lower while Zn, Cr, Cd and Pb contents are higher than the crustal average values. The high values draw attention to the land-based domestic and industrial inputs. Lake Terkos sediments have high enrichment factors (EF) of Zn, Cr, Cd and Pb metals which corroborate this result. The low EFs of Fe, Ni and Cu are due to the natural (terrigeneous) inputs. Additionally, there is no Al, Fe, Ni and Cu metal enrichment in these lake sediments because of the low contamination factor (CF) values. However, it is moderately contaminated by Zn, Cr and Pb, and heavily contaminated by Cd.     

Determination of heavy metals and metals levels in five fish species from I??kl? Dam Lake and Karaca?ren Dam Lake (Turkey)

The concentrations of heavy metals and metals (Zn, Pb, Bi, Cd, Ni, Co, Fe, Mn, Mg, Cu, Cr, Ca, Sr, Na, Li, K) were measured in muscle of five species Cyprinus carpio (from I??kl? dam), Scardinius erythrophthalmus (from I??kl? dam), Tinca tinca (from I??kl? dam), C. carpio (from Karaca?ren dam), Carassius carassius (from Karaca?ren dam) caught from I??kl? and Karaca?ren. The highest metal was Na (466.95 μg/g) in C. carassius, while the lowest levels were Fe (0.37 μg/g) and Cu (0.37 μg/g) in C. carpio from I??kl? dam. The mean concentrations μg/g d.w. some of heavy metals in muscle of C. carpio (from I??kl? dam), S. erythrophthalmus (from I??kl? dam), T. tinca (from I??kl? dam), C. carpio (from Karaca?ren dam), C. carassius (from Karaca?ren dam) were as follows: Cd 2.00-2.10-1.95-2.06-2.27, Zn 4.36-2.64-13.13-13.33-24.47, Pb 1.65-1.24-1.90-2.37-2.41, Co 2.46-2.37-2.48-2.58-2.80, Mg 138.51-154.35-218.59-204.58-202.16, Fe 0.37-2.62-3.17-3.01-12.33, respectively.     

Assessment of potential health risk for inhabitants living near a former lead smelter. Part 1: metal concentrations in soils, agricultural crops, and homegrown vegetables

Soil contamination by metals engenders important environmental and health problems in northern France where a smelter (Metaleurop Nord) was in activity for more than a century. This study aims to look at the long-term effects of the smelter after its closedown by combining data on the degree of soil contamination and the quality of the crops grown (agricultural crops and homegrown vegetables) in these soils for a better assessment of the local population’s exposure to Cd, Pb, and Zn. Seven years after the Metaleurop Nord closedown, (1) the agricultural and urban topsoils were strongly contaminated by Cd, Pb, and Zn; (2) the kitchen garden topsoils were even more polluted than the agricultural soils, with great variability in metal concentrations within the gardens studied; (3) a high proportion of the agricultural crops for foodstuffs did not conform with the European legislation; (4) for feedstuffs, most samples did not exceed the Cd and Pb legislation limits, indicating that feedstuffs may be an opportunity for most agricultural produce; and (5) a high proportion of the vegetables produced in the kitchen gardens did not conform with the European foodstuff legislation. The high contamination level of the soils studied continues to be a risk for the environment and the population’s health. A further investigation (part 2) assesses the associated potential health risk for local inhabitants through consumption of homegrown vegetables and ingestion of soil particles by estimating the site-specific human health assessment criteria for Cd and Pb.     

Simplified determination of lipophilic metabolites of nonylphenol ethoxylates: method development and application in aqueous samples from Buenos Aires, Argentina

In the present work we have developed an analytical methodology for the determination of nonylphenol (NP) and nonylphenol mono- and di-ethoxylates (NP1EO and NP2EO) in water samples. The applicability of this methodology was proved by means of the analysis of environmentally relevant aqueous samples from Buenos Aires. This constitutes a starting point for a rigorous assessment of the incidence of NPnEO surfactants in Argentina, as only very few, qualitative or semi-quantitative data on the occurrence of these compounds in local systems were available up to this time. Enrichment of the analytes was carried out by solid-phase extraction on a C-18 sorbent, followed by elution with ethyl acetate. Normal-phase high performance liquid chromatography on an amino-silica column and fluorescence detection at excitation-emission wavelengths of 230-300 nm were employed for separation and quantification of the analytes. Confirmation of peak assignment in selected real samples was performed by off-line coupling HPLC with GC-MS analysis. A non-polar GC capillary column was used, and a characteristic peak pattern was obtained for the alkyl chain isomers of each ethoxylated homologue and NP. GC-MS analyses yielded in all cases purity levels higher than 80% for the HPLC collected fractions. The elevated concentrations found for the estrogenic metabolites of NPnEO are in accordance with an unrestricted use of this class of non-ionic surfactants in the country.     

The comparison of heavy metal accumulation ratios of some fish species in Enne Dame Lake (Kütahya/Turkey)

The metal accumulation levels for muscle, skin, gill, liver and intestine tissues of some Cyprinidae species (Carassius carassius, Condrostoma nasus, Leuciscus cephalus and Alburnus alburnus) in Enne Dame Lake (Kütahya/Turkey), which is mostly fed by hot spring waters, were investigated. Analyses were performed for copper (Cu), zinc (Zn), manganese (Mn), iron (Fe), cobalt (Co), magnesium (Mg), nickel (Ni), chrome (Cr) and boron (B) using inductively coupled plasma-optic emission spectroscopy (ICP-OES), and cadmium (Cd) using atomic absorption spectrophotometer (AAS) utilizing microwave digestion techniques. The concentrations of the heavy metals found in the fish varied in the follow ing ranges: Cu: < DL-7.04, Zn: 6.96-357.25, Mn: < DL-20.70, Ni: < DL-6.21, Fe: 9.62-2500.33, Cr: < DL-1.74, Co: < DL-0.54, Cd: 0.01-0.27 and Mg: 197.44-904.90 mg/kg wet weight. While B had the second highest concentration in the water of the lake, it was not encountered in any tissue of the investigated species. In all tissues and the species, While the bioaccumulation factors (BAFs) of Mn, Zn, Fe and Cu were remarkably high, the BAFs of Mg, Cr, Co, and B were also fairly low or none. Although the heavy metal accumulation levels for the muscle were generally lower than other tissues, there were some exceptions. Cd level in the muscle of C. carassius was higher than the permissible limit stated by Turkish legislation, FAO and WHO. The mean metal amounts for all the investigated tissues and species are statistically compared and discussed in this study.