Levels of ²¹⁰Po and ²¹⁰Pb in fish and molluscs in Slovenia and the related dose assessment to the population

²¹⁰Po and ²¹⁰Pb activity concentrations in fish from the Slovenian part of Adriatic Sea, in the vicinity of a former uranium mine at ?irovski vrh and from the Slovenian market were determined. In addition, ²¹⁰Po and ²¹⁰Pb activity concentrations in squid from the Slovenian market and in mussels from the Slovenian part of the Adriatic Sea were also determined. Fish, squid and mussel consumption in Slovenia was assessed from the data available from Eurostat and Food and Agriculture Organisation (FAO) and the data used for the corresponding dose calculation. Fish species with the highest activity concentrations were grilled to assess possible loss of ²¹⁰Po during the food preparation process. Samples were freeze dried and radiochemical separation of ²¹⁰Po and ²¹⁰Pb was performed. Measurements of ²¹⁰Po were performed by alpha spectrometry and ²¹⁰Pb by a low background gas-flow proportional counter. ²¹⁰Po activity concentrations in fish, squid and mussels were from 0.039 to 35.0 Bq kg⁻¹ fresh weight and ²¹⁰Pb activity concentrations were from 0.08 to 3.03 Bq kg⁻¹ fresh weight. Grilling of fish resulted in no significant loss of ²¹⁰Po at 90 °C. The assessed combined annual effective ingestion dose due to ²¹⁰Po and ²¹⁰Pb for fish, squid and mussels consumed in Slovenia is 47.6 μSv year⁻¹.     

Leaching and persistence of ametryn and atrazine in red–yellow latosol

This study evaluated the mobility and persistence of atrazine and ametryn in red–yellow latosols using polyvinyl chloride columns with a diameter of 100 mm and a height of 15 cm. The assays simulated 60-mm rainfall events at 10-day intervals for 70 days. The persistence and leaching were evaluated for these two herbicides. The analytes obtained from the samples were quantified by gas chromatography using flame ionization detection. Compared with ametryn, atrazine showed a greater potential to reach depths below 15 cm over 30 days of simulated rain. Ametryn, however, showed greater persistence in soil at 70 days after application. The persistence of atrazine and ametryn in soil under sunlight was 10 and 144 days respectively. Atrazine was more susceptible to sunlight than ametryn because sunlight favored atrazine degradation in hydroxyatrazine. The results indicate that in red–yellow latosol, atrazine has a high leaching potential in short term, but that ametryn is more persistent and has a high leaching potential in long term.     

17 β-estradiol mineralization in human waste products and soil in the presence and the absence of antimicrobials

Natural steroidal estrogens, such as 17 β-estradiol (E2), as well as antimicrobials such as doxycycline and norfloxacin, are excreted by humans and hence detected in sewage sludge and biosolid. The disposal of human waste products on agricultural land results in estrogens and antibiotics being detected as mixtures in soils. The objective of this study was to examine microbial respiration and E2 mineralization in sewage sludge, biosolid, and soil in the presence and the absence of doxycycline and norfloxacin. The antimicrobials were applied to the media either alone or in combination at total rates of 4 and 40 mg kg^?1, with the 4 mg kg^?1 rate being an environmentally relevant concentration. The calculated time that half of the applied E2 was mineralized ranged from 294 to 418 days in sewage sludge, from 721 to 869 days in soil, and from 2,258 to 14,146 days in biosolid. E2 mineralization followed first-order and the presence of antimicrobials had no significant effect on mineralization half-lives, except for some antimicrobial applications to the human waste products. At 189 day, total E2 mineralization was significantly greater in sewage sludge (38 ±0.7%) > soil (23 ±0.7%) > biosolid (3 ±0.7%), while total respiration was significantly greater in biosolid (1,258 mg CO₂) > sewage sludge (253 mg CO₂) ≥ soil (131 mg CO₂). Strong sorption of E2 to the organic fraction in biosolid may have resulted in reduced E2 mineralization despite the high microbial activity in this media. Total E2 mineralization at 189 day was not significantly influenced by the presence of doxycycline and/or norfloxacin in the media. Antimicrobial additions also did not significantly influence total respiration in media, except that total CO₂ respiration at 189 day was significantly greater for biosolid with 40 mg kg^?1 doxycycline added, relative to biosolid without antimicrobials. We conclude that it is unlikely for doxycycline and norfloxacin, or their mixtures, to have a significant effect on E2 mineralization in human waste products and soil. However, the potential for E2 to be persistent in biosolids, with and without the presence of antimicrobials, is posing a challenge for biosolid disposal to agricultural lands.     

Characterizing changes in surface ozone levels in metropolitan and rural areas in the United States for 1980–2008 and 1994–2008

In this analysis, we characterize urban and rural ozone (O₃) trends across the US for the periods 1980–2008 (29 years) and 1994–2008 (15 years) using three exposure metrics, which summarize daily O₃ concentrations to reflect different ways O₃ may affect human health and vegetation. We observe that a statistically significant trend at a specific monitoring site, using one exposure metric, does not necessarily result in a similar trend using the other two metrics. The two most common trends among the monitoring sites are either a continuation of negative trending over the 29-year period or a shift from negative to no trend status, indicating a leveling off of the trending. Very few sites exhibit statistically significant increases in the exposure indices. In characterizing the statistically significant changes in the distribution of hourly average O₃, we observe subtle statistically significant changes in the lower part of the distribution (i.e., below 50 ppb) that are not necessarily captured by the trending patterns associated with the three exposure metrics. Using multisite data from 12 metropolitan cities, we find that as the frequency of higher hourly average concentrations is reduced, the lower hourly average concentrations also move upward toward the mid-level values. The change in the number of the hourly average concentrations in the lower range is consistent with decreased NO scavenging. We recommend assessing possible subtle shifts in O₃ concentrations by characterizing changes in the distribution of hourly average concentrations by month. Identifying statistically significant monthly changes in the mid- and low-level hourly average concentrations may provide important information for assessing changes in physical processes associated with global climate change, long-range transport, and the efficacy of models used for emission and risk reductions. Our results indicate that it is important to investigate the change in the trending pattern with time (e.g., moving 15-year trending) in order to assess how year-to-year variability may influence the trend calculation.     

Persistence and Changes in Bioavailability of Dieldrin, DDE, and Heptachlor Epoxide in Earthworms Over 45 Years

The finding of dieldrin (88 ng/g), DDE (52 ng/g), and heptachlor epoxide (19 ng/g) in earthworms from experimental plots after a single moderate application (9 kg/ha) 45 years earlier attests to the remarkable persistence of these compounds in soil and their continued uptake by soil organisms. Half-lives (with 95 % confidence intervals) in earthworms, estimated from exponential decay equations, were as follows: dieldrin 4.9 (4.3–5.7) years, DDE 5.3 (4.7–6.1) years, and heptachlor epoxide 4.3 (3.8–4.9) years. These half-lives were not significantly different from those estimated after 20 years. Concentration factors (dry weight earthworm tissue/dry weight soil) were initially high and decreased mainly during the first 11 years after application. By the end of the study, average concentration factors were 1.5 (dieldrin), 4.0 (DDE), and 1.8 (heptachlor epoxide), respectively.     

Analysis of organochlorine pesticide residues in human and cow’s milk in the towns of Asendabo,Serbo and Jimma in South-Western Ethiopia

The level of some OCPs in human and cow milk collected from Asendabo, Serbo and Jimma in South-West Ethiopia were analyzed using GC–ECD. Results of the analysis indicated that all samples contained detectable quantities of p,p′-DDT and its metabolites, p,p-DDE and p,p-DDD, but none of the other OCPs analyzed. Mean levels of total DDT in the human and cow milk samples in the three areas were 12.68 and 0.389 μg g^?1 respectively. The distributions of p,p-DDT, p,p-DDE and p,p-DDD in the human milk samples from the three locations followed the same trend in which the proportion of p,p-DDT was the highest in all the three cases, comprising 55–71% of total DDT, followed by p,p-DDE, 26–39%, and the least, p,p-DDD of 2–5%. The mean ratio of DDT/DDE concentration for the three areas was calculated to be 2.01. This value was much higher than the values reported from other countries in earlier studies and indicates the existence of a higher quantity of DDT from a fresh input in the three study areas. The mean estimated daily intake of DDT by infants from mother’s milk in the three locations was found to be 62.17 μg kg^?1 body weight, which is about three times higher than the acceptable daily intake set by WHO/FAO for total DDT, 20 μg kg^?1 of body weight. This alarmingly high daily intake value is a cause for concern, since children are highly susceptible to effects from such environmental contaminants. The study has revealed that people in the study areas are facing exposure to DDT from recent use. The observed contamination of mother’s milk and the possible transfer of the contaminant from mother to child is an obvious risk associated with breast-feeding in the study areas and possibly in other parts of the country too.     

Microbiota’s role in health and diseases

Environmental Science and Pollution Research - The microbiome is a term that usually refers to the community of various microorganisms that inhabit/live inside human/animal bodies or on their skin....     

Organic matter in the bulk precipitations in Zagreb and Šibenik,Croatia

Dissolved organic carbon (DOC), surface active substances (SAS) and copper complexing capacity (CuCC) were studied in bulk precipitations collected periodically from 2003 to 2007 in the continental city of Croatia (Zagreb: n = 27) and in the city at the Adriatic coast (?ibenik: n = 38). DOC concentrations (Zagreb: 0.67–4.03 mgC/L with average concentration of 1.93 ± 0.76 mgC/L; ?ibenik: 0.44–4.13 mgC/L with average concentration of 1.83 ± 0.83 mgC/L) are similar to those measured in other samples of continental rainwater in the northern hemisphere. The concentrations of SAS in samples from Zagreb ranged from 0.055 to 0.45 eq. Triton-X-100 mg/L with average concentration of (0.14 ± 0.06) eq. Triton-X-100 mg/L. SAS fractions were of a similar range in ?ibenik (0.02–0.60 eq. Triton-X-100 mg/L) with an average concentration of 0.11 ± 0.06 eq. Triton-X-100 mg/L. However, the lowest values of SAS (between 0.02 and 0.04 eq. Triton-X-100 mg/L) were observed only in ?ibenik (27%). We have estimated that the higher pH values were responsible for lower surface activity of organic matter in bulk samples from ?ibenik. DOC may form complexes that control the transport and solubility of heavy metals in natural water. CuCC measured in ?ibenik in the range 0.066–1.4 μM Cu²⁺ was in general higher, compared to the one in Zagreb (0.010–0.586 μM Cu²⁺) which is the result of biogenically driven organic contribution to the precipitation, especially in the warmer period of the year.     

Persistence and transport of bacteria and viruses in groundwater — a conceptual evaluation

The results of an interdisciplinary research program on the subsurface persistence and transport of pathogenic bacteria and viruses are evaluated on the basis of an expanded advection-dispersion model which considers the persistence of these microorganisms under the conditions found within an aquifer, the retardation by adsorption-desorption processes and the role of filtration processes. The model indicates that the principal controls are filtration processes, the microorganisms being fixed on the filter media are ultimately eliminated or inactivated by biological, chemical and physical processes.     

17 β-estradiol and 17 α-ethinylestradiol mineralization in sewage sludge and biosolids

Natural steroid estrogens (e.g., 17 β-estradiol, E2), synthetic steroid estrogens (e.g., 17 α-ethinylestradiol, EE2) and pharmaceutical antibiotics (e.g., ciprofloxacin) are chemicals detected in biosolids and sewage sludges because they partition into the solids fraction during the wastewater treatment process. This research utilized a three-way factorial design (six media × two estrogens × three antibiotic treatments) to quantify cumulative E2 and EE2 mineralization over 133 d (MAX) in a range of sewage sludge and biosolid samples in the presence (4 and 40 mg kg^?1) and absence of ciprofloxacin. The same three-way factorial design was utilized to quantify the impact of the six media, E2 or EE2, and ciprofloxacin on cumulative soil respiration over 133 d (RESP). Minimal ciprofloxacin mineralization was observed (<0.05% over 133 d), but despite its persistence, ciprofloxacin had no significant effect on MAX of E2 or EE2, and, in general, no significant effect on RESP. MAX ranged from 38.38% to 48.44% for E2 but from only 0.72% to 24.27% for EE2 although RESP was relatively similar, ranging from 101.00 to 866.54 mg CO₂ in the presence of E2 and from 69.55 to 893.95 mg CO₂ in the presence of EE2. The sorption-limited bioavailability of EE2, which is inherently resistant to biodegradation due to chemical structure, as MAX and Freundlich sorption coefficients (K_f) were negatively correlated. As such, the K_f values of EE2 were largest in composted biosolids in which EE2 was particularly resistant to microbial degradation as the MAX of EE2 was <3%. In contrast, the MAX of E2 showed a positive association with the K_f values of E2 because some steps in the E2 transformation process have been found to occur in the sorbed phase. The MAX of E2 was significantly greater in the biosolid and composted biosolid media than in any other media, whereas the MAX of E2 decreased in the following order: secondary sewage sludge > primary sewage sludge > biosolid = composted biosolid. This suggests that sewage sludges in municipal lagoons and pre-treatment holding lagoons are a more favorable media for mineralization of EE2, whereas biosolids in post-treatment storage lagoons are a more favorable media for the mineralization of E2. The presence of ciprofloxacin will have no impact on the potential E2 or EE2 mineralization rates in these cases.     

Estimation of β-cyfluthrin and imidacloprid in okra fruits and soil by chromatography techniques

Dissipation of β-cyfluthrin and imidacloprid in okra was studied following three applications of a combination formulation of Solomon 300 OD (β-cyfluthrin 9 % + imidacloprid 21 %) @ 60 and 120 g a.i. ha(-1) at 7 days interval. Residues of β-cyfluthrin and imidacloprid in okra were estimated by gas liquid chromatography (GLC) and high performance liquid chromatography (HPLC), respectively. Residues of β-cyfluthrin were confirmed by gas chromatograph-mass spectrometry (GC-MS) and that of imidacloprid by high performance thin layer chromatography (HPTLC). Half-life periods for β-cyfluthrin were found to be 0.91 and 0.68 days whereas for imidacloprid these values were observed to be 0.85 and 0.96 days at single and double the application rates, respectively. Residues of β-cyfluthrin dissipated below its limit of quantification (LOQ) of 0.01 mg kg(-1) after 3 and 5 days at single and double the application dosage, respectively. Similarly, residues of imidacloprid took 5 and 7 days to reach LOQ of 0.01 mg kg(-1), at single and double dosages respectively. Soil samples collected after 15 days of the last application did not show the presence of β-cyfluthrin and imidacloprid at their detection limit of 0.01 mg kg(-1).     

Biodegradation of α and β isomers of endosulphan and endosulphan sulphate in Indian soils

Abstract

The degradation of α and β isomers of endosulphan and endosulphan sulphate in four sterilized and non sterilized Indian soils under laboratory conditions was studied. Degradation was found to be more in non‐sterilized as compared to the sterilized soil. The half life of α‐endosulphan, β‐endosulphan and endosulphan sulphate was found to be 136.8, 273 and 301 days in sterilized Alfisol and 55, 256 and 277 days in non‐sterilized Alfisol, respectively. α‐Endosulphan degraded more readily than β‐endosulphan and endosulphan sulphate under both sterilized and non‐sterilized soil conditions.     

Estimation of β-cyfluthrin and imidacloprid in okra fruits and soil by chromatography techniques

Dissipation of β-cyfluthrin and imidacloprid in okra was studied following three applications of a combination formulation of Solomon 300 OD (β-cyfluthrin 9 % + imidacloprid 21 %) @ 60 and 120 g a.i. ha^?1 at 7 days interval. Residues of β-cyfluthrin and imidacloprid in okra were estimated by gas liquid chromatography (GLC) and high performance liquid chromatography (HPLC), respectively. Residues of β-cyfluthrin were confirmed by gas chromatograph–mass spectrometry (GC-MS) and that of imidacloprid by high performance thin layer chromatography (HPTLC). Half-life periods for β-cyfluthrin were found to be 0.91 and 0.68 days whereas for imidacloprid these values were observed to be 0.85 and 0.96 days at single and double the application rates, respectively. Residues of β-cyfluthrin dissipated below its limit of quantification (LOQ) of 0.01 mg kg^?1 after 3 and 5 days at single and double the application dosage, respectively. Similarly, residues of imidacloprid took 5 and 7 days to reach LOQ of 0.01 mg kg^?1, at single and double dosages respectively. Soil samples collected after 15 days of the last application did not show the presence of β-cyfluthrin and imidacloprid at their detection limit of 0.01 mg kg^?1.     

Behaviour and dynamics of di-ammonium phosphate in bauxite processing residue sand in Western Australia—II. Phosphorus fractions and availability

Background, aim and scope  

Australia is the largest producer of bauxite in the world, with an annual output of approximately 62 million metric dry tons in 2007. For every tonne of alumina, about 2 tonnes of highly alkaline and highly saline bauxite-processing residue are produced. In Western Australia, Alcoa World Alumina, Australia (Alcoa) produces approximately 15 MT of residue annually from its refineries (Kwinana, Pinjarra and Wagerup). The bauxite-processing residue sand (BRS) fraction represents the primary material for rehabilitating Alcoa’s residue disposal areas (RDAs). However, the inherently hostile characteristics (high alkalinity, high salinity and poor nutrient availability) of BRS pose severe limitations for establishing sustainable plant cover systems. Alcoa currently applies 2.7 t ha⁻¹ of di-ammonium phosphate ((NH₄)₂HPO₄; DAP)-based fertiliser as a part of rehabilitation of the outer residue sand embankments of its RDAs. Limited information on the behaviour of the dominant components of this inorganic fertiliser in highly alkaline BRS is currently available, despite the known effects of pH on ammonium (NH₄) and phosphorus (P) behaviour. The aim of this study was to quantify the effects of pH on NH₃ volatilisation and residual nitrogen (N) in BRS following DAP applications.     

Amino acids in dew – origin and seasonal variation

At two sites in the Armenhof district, 10 km east of Fulda, Germany, dew samples were collected from June 1996 to June 1997 and investigated for free and protein-bound amino acids. On account of the high pollen content, at the beginning of June 1996 and in May 1997 total amino acid concentrations were 53–390 μmol l⁻¹, in one sample 922 μmol l⁻¹. At other times the concentration in dew was 8–164 μmol l⁻¹. On 4 and 5 June 1996 the diluted free amino acid fraction (DFAA) of the total hydrolysed amino acids (THAA) at both sites amounted to 35–44% and was predominantly arginine, proline and glutamine/glutamate. Likewise on 11 March 1997 the fraction of DFAA was found to be 39.5% with extremely high arginine and proline fractions. At other times the DFAA-fraction was in the range 14–26%. From July 1996 to June 1997 the amino acid concentrations in the vapours rising from a meadow were also measured and it ranged from 8 to 51 μmol l⁻¹. From July to October 1996 the amino acid composition in the hydrolysates of dew samples and meadow vapours collected overnight were almost identical. The DFAA fraction in the condensation water collected overnight from the meadow varied from 18 to 40%. From 4 to 6 June 1996, on 11 and 13 March 1997 and in the period 16–20 May 1997, the amino acid distribution in dew showed much variation. The percentage fraction of arginine and proline in the hydrolysate increased greatly, whereas that of glycine and serine decreased. The large increase in proline and arginine in hydrolysate is attributable solely to the large amounts of free arginine and proline. This effect occurred in both 1996 and 1997 over several days at both sites at any one time and therefore appears confirmed.     

Distribution of total mercury and methylmercury in lake sediments in Arctic Ny-Ålesund

The toxicities and bioavailabilities of total mercury (THg) and methylmercury (MeHg) in aquatic systems have made them the subjects of recent research. In this study, we collected a lake sediment core from Ny-Ålesund in Svalbard and analyzed the distributions of THg and MeHg in the sediments. The increased trend of THg was caused by anthropogenic contamination since the 14th century through long-range transportation, especially after the industrial era. However, the peak values of Hg in surface sediment samples could be explained by the increased algal scavenging process in recent decades. All the biogeochemical proxies (e.g., pigments and diatom biomass) revealed recent sharp increases in aquatic primary production due to the current climate warming. Rock-Eval analyses indicated that algal-derived organic matter took up a large portion, and quantitative calculation showed that 89.6-95.8% of the Hg in post-1950 could be explained by scavenging. The distribution of MeHg has a close relationship with total Hg and organic matter. The oxidation-reduction condition is one of the possible factors affecting the methylation rates in H2 lake sediments. Higher algal productivity and organic matter actually led to the increased trend of methylation in the uppermost sediment. This study supports some new key hypotheses on climate-driven factors affecting Hg and MeHg cycling in High Arctic lake sediments.     

Distribution of Hg,As and Se in material and flue gas streams from preheater–precalciner cement kilns and vertical shaft cement kilns in China

The aim of this study was to evaluate the behavior of Hg, As, and Se in cement production. Two types of cement plants were studied, including the vertical shaft kiln (VSK) and preheater–precalciner kiln (PPK) processes. Determination of Hg, As, and Se in the main material and gas streams were performed. It was found that recycling of particulate matter captured by an air pollution control device caused a significant enrichment of Hg and As inside both processes. The total quantity of Hg entering the process and the quantity emitted to the atmosphere were found to be 10–109 and 6.3–38 mg, respectively, per ton of clinker produced. The average Hg emission was calculated to be around 41% of the total mercury input. The emissions found complied with the European Union (EU) limit and exceeded partly the U.S. limit. Furthermore, it was found that oxidized mercury was the dominant species in the PPK process, whereas the reduced form was dominant in the VSK process, due to the oxidizing and reducing gas conditions, respectively. Regarding the distribution of As and Se, the major amounts were bound to the solid materials, that is, cement clinker and particulate matter. Based on cement production data in China in 2013, the annual emissions of Hg and As were estimated to be in the range of 8.6–52 and 4.1–9.5 tons, respectively.

Implications: There are fairly limited studies on Hg, As, and Se measurements from cement manufacturing facilities in China, and even more limited studies on the behavior in vertical shaft kilns. The needs for increased emission reduction efforts in energy-intensive industries are globally recognized, and an improved understanding of the processes ongoing in a cement kilns system is decisive. Since the processes are complex and almost impossible to recreate in the laboratory, field measurements are indeed important. The findings in the present study were solely based on field measurements and the data are considered to be valuable for the further development of emission reduction technology.     

Polyfluoroalkyl phosphate esters and perfluoroalkyl carboxylic acids in target food samples and packaging—method development and screening

Polyfluoroalkyl phosphate mono-, di-, and tri-esters (mono-, di-, and triPAPs) are used to water- and grease-proof food packaging materials, and these chemicals are known precursors to perfluoroalkyl carboxylic acids (PFCAs). Existing analytical methods for PAPs lack sample clean-up steps in the sample preparation. In the present study, a method based on ultra performance liquid chromatography coupled to tandem mass spectrometry (UPLC/MS/MS) was developed and optimized for the analysis of mono-, di-, and triPAPs, including a clean-up step for the raw extracts. The method was applied to food samples and their PAP-containing packaging materials. The optimized UPLC/MS/MS method enabled the separation and identification of a total of 4 monoPAPs, 16 diPAPs, and 7 triPAPs in the technical mixture Zonyl®-RP. For sample clean-up, weak anion exchange solid phase extraction columns were tested. PAPs standard solutions spiked onto the columns were separated into a fraction containing neutral compounds (triPAPs) and a fraction with ionic compounds (mono- and diPAPs) with recoveries between 72–110 %. Method limits of quantification for food samples were in the sub to low picogram per gram range. For quantitative analysis of PAPs, compound-specific labeled internal standards showed to be essential as sorption and matrix effects were observed. Mono-, di-, and/or triPAPs were detected in all food packaging materials obtained from the Swedish market. Up to nine diPAPs were detected in the food samples, with the 6:2/6:2 and 6:2/8:2 diPAPs as the dominant compounds. DiPAP concentrations in the food samples ranged from 0.9 to 36 pg/g, which was comparable to individual PFCA concentrations in the same samples. Consumption of food packed in PAP-containing materials could be an indirect source of human exposure to PFCAs.