Concentrations and speciation of arsenic in groundwater polluted by warfare agents

Groundwater polluted with phenylarsenicals from former warfare agent deposits and their metabolites was investigated with respect to the behavior of relevant arsenic species. Depth profiles at the estimated source and at about 1 km downgradient from the source zone were sampled. The source zone is characterized by high total arsenic concentrations up to 16 mg L⁻¹ and is dominated by organic arsenic compounds. The concentrations in the downgradient region are much lower (up to 400 μg L⁻¹) and show a high proportion of inorganic arsenic species. Iron precipitation seems to be an effective mechanism to prevent dispersion of inorganic arsenic as well as phenylarsonic acid. Reductive conditions were observed in the deeper zone with predominant occurrence of trivalent arsenic species. The inorganic species are in redox equilibrium, whereas the phenylarsenic compounds have variable proportions. Methylphenylarsinic acid was identified in groundwater in traces which indicates microbial degradation activity.     

Cross-sectional biomonitoring study of pesticide exposures in Queensland,Australia, using pooled urine samples

A range of pesticides are available in Australia for use in agricultural and domestic settings to control pests, including organophosphate and pyrethroid insecticides, herbicides, and insect repellents, such as N,N-diethyl-meta-toluamide (DEET). The aim of this study was to provide a cost-effective preliminary assessment of background exposure to a range of pesticides among a convenience sample of Australian residents. De-identified urine specimens stratified by age and sex were obtained from a community-based pathology laboratory and pooled (n = 24 pools of 100 specimens). Concentrations of urinary pesticide biomarkers were quantified using solid-phase extraction coupled with isotope dilution high-performance liquid chromatography–tandem mass spectrometry. Geometric mean biomarker concentrations ranged from <0.1 to 36.8 ng/mL for organophosphate insecticides, <0.1 to 5.5 ng/mL for pyrethroid insecticides, and <0.1 to 8.51 ng/mL for all other biomarkers with the exception of the DEET metabolite 3-diethylcarbamoyl benzoic acid (4.23 to 850 ng/mL). We observed no association between age and concentration for most biomarkers measured but noted a “U-shaped” trend for five organophosphate metabolites, with the highest concentrations observed in the youngest and oldest age strata, perhaps related to age-specific differences in behavior or physiology. The fact that concentrations of specific and non-specific metabolites of the organophosphate insecticide chlorpyrifos were higher than reported in USA and Canada may relate to differences in registered applications among countries. Additional biomonitoring programs of the general population and focusing on vulnerable populations would improve the exposure assessment and the monitoring of temporal exposure trends as usage patterns of pesticide products in Australia change over time.     

A technical mixture of 2,2',4,4'-tetrabromo diphenyl ether (BDE47) and brominated furans triggers aryl hydrocarbon receptor (AhR) mediated gene expression and toxicity

Polybrominated diphenyl ethers (PBDE) are found as ubiquitous contaminants in the environment, e.g., in sediments and biota as well as in human blood samples and mother's milk. PBDEs are neuro- and developmental toxins, disturb the endocrine system and some are even carcinogenic. Structural similarities of PBDEs with dioxin-like compounds, e.g., 2,3,7,8-tetrachloro-dibenzodioxin (TCDD), have raised concern about a possible "dioxin-like" action of PBDEs. TCDD exerts its toxicity via binding to and activation of the aryl hydrocarbon receptor (AhR). AhR ligands are in contrast to PBDEs usually coplanar compounds. Thus, PBDEs are not likely to be strong AhR agonists. The aim of this study was to analyze the effects of the most abundant PBDE congener, 2,2',4,4'-tetrabromo diphenyl ether (BDE47), on AhR activity and signaling. Initially, we measured cytochrome P450 1A1 (Cyp1A1) induction as a readout for AhR activation by BDE47. Low grade purified BDE47 increased CYP1A1 levels in transformed and primary rat hepatocytes and human hepatoma cells. Chemical analysis of the BDE47 sample identified trace contaminations with brominated furans such as 2,3,7,8-tetrabromo dibenzodioxin (TBDF), which most likely were responsible for the observed activation of AhR. Subsequently, the BDE47 mixture was studied for its effect on AhR mediated toxicity and global gene expression. Indeed, in rat hepatoma cells and in zebrafish embryos the BDE47 mixture provoked changes in gene expression and toxicity similar to known AhR agonists. In addition to the dioxin-like actions, the BDE47 sample enhanced Cyp2B and Cyp3A expression suggesting that commercial PBDE mixtures, which also often contain brominated furans, may disturb cellular homeostasis at multiple levels.     

Evaluation of land use and water quality in an agricultural watershed in the USA indicates multiple sources of bacterial impairment

Pathogens are the number one cause of impairments of assessed rivers and streams in the USA and pose a significant human health hazard. The Dry Run Creek Watershed in Northeast Iowa has been designated as impaired by the State of Iowa because of high levels of Escherichia coli bacteria. To investigate the nature of this impairment, land use and stream bank assessments were coupled with comprehensive water quality monitoring. Physical, chemical, and biological parameters were measured at 13 different sites in the watershed, including pH, temperature, conductivity, dissolved oxygen, turbidity, total Kjeldahl nitrogen, ammonia-N, nitrate?+?nitrite-N, total phosphorus, and E. coli. In addition, benthic macroinvertebrate communities were analyzed at seven sites, and optical brightener tests were performed late in the season. Results identified segments of the watershed that were more prominent contributors of E. coli, and correlations were observed between levels of E. coli and several chemical parameters, including ammonia-N, total Kjeldahl nitrogen, and total phosphorus. Interestingly, distinct sites emerged as more prominent contributors of these elements during rain vs. non-rain events, suggesting different types of sources. Both the amount of rainfall and the time elapsed between the rain event and the sampling influenced E. coli levels during wet weather conditions. Nitrate?+?nitrite-N displayed a unique response to rain events compared with the other parameters, suggesting a different delivery route. Analyses of benthic macroinvertebrate communities were consistent with pollution trends. Collectively, these data suggest distinct agriculturally related E. coli contributions, as well as specific areas and practices for water quality improvement strategies. This study can serve as a resource for evaluating agricultural watersheds that are impaired for bacteria.     

Determination of heavy metals in bee honey with connected and not connected metal wires using inductively coupled plasma atomic emission spectrometry (ICP–AES)

Two honey samples are taken from two parts of the same honeycomb: one that contacts to the surface of the wire and the other taken from the surface that does not contact the wires. Heavy metal contents of these two samples were determined by inductively coupled plasma atomic emission spectrometry). The Mo, Cd, Cr, Fe, Mn, Ni and Zn contents of the honey in contact with wire is higher when compared to the other. Especially, Fe and Zn contents of honey in contact with wire is much higher than the non-contact one. These values are, respectively, 190.21 and 112.76 ppm. Besides, Ni content of honey in contact with wire is approximately 50% higher.     

Persistence,variance and toxic levels of organochlorine pesticides in fluvial sediments and the role of black carbon in their retention

The present study assesses the persistence and variation of organochlorine pesticides (OCPs) and their regulation by total organic carbon (TOC) and black carbon (BC) in freshwater sediment. Sediment samples from the Yamuna River, a major tributary of the Ganges (one of the most populated and intensively used rivers in Asia), had high levels of Σ₂₀OCPs (21.41 to 139.95 ng g^?1). β-Hexachlorocyclohexane (β-HCH) was the most predominant component. ΣHCH and Σdichloro-diphenyl-trichloroethane (DDT) constituted ~86 % of Σ₂₀OCPs. Isomer ratios indicated fresh usage of lindane, DDT and technical-grade HCH. Toxicological comparison with freshwater sediment quality guidelines showed γ-HCH and DDT at high levels of concern. β-HCH, α-HCH, endrin, heptachlor epoxide, dichloro-diphenyl-dichloroethane (DDD), dichloro-diphenyl-dichloroethylene and chlordane were above some of the guideline levels. TOC and BC had mean concentrations of 1.37?±?0.51 % and 0.46?±?0.23 mg g^?1, respectively. BC constituted 1.25 to 10.56 % of TOC. We observed low to moderate correlations of BC with isomers of HCH, p,p′-DDT and methoxychlor while of TOC with Σ₂₀OCPs, γ-HCH, endosulfan sulfate and methoxychlor. Principal component analysis enabled correlating and clustering of various OCPs, BC and TOC. OCP distribution was related with pH, electrical conductivity, soil moisture and finer fractions of sediment. OCPs with similarity in properties that determine their interactions with carbonaceous components of sediment clustered together. A number of factors may, thus, be involved in the regulation of interactive forces between BC and OCPs. BC in this study may be more important than TOC in the retention of some OCPs into fluvial sediments, thereby reducing their bioavailability. The finding is probably the first of its kind to report and emphasises the role of BC in the persistence of OCPs in fluvial sediments.     

Using Fiber Optics to Detect Moisture Intrusion into a Landfill Cap Consisting of a Vegetative Soil Barrier

Abstract

The intrusion of moisture into landfills can pose a health hazard because of the possibility that the moisture will carry harmful substances into the groundwater. Early detection of moisture anywhere within these landfills is essential if corrective action is to be taken well before an occurrence of this kind. This paper presents the results of a field-scale simulation test of the use of fiber optics to detect the presence of moisture within landfill covers, using a detection method based on the thermal response of soils as a function of their moisture content. By sending electrical current through an embedded stainless-steel tube, soils of varying moisture content were heated and time-dependent temperature measurements were obtained with a fiber-optic distributed temperature sensor system. The optical fiber itself lay within the tube, but its temperature was a function of how rapidly heat was conducted into the surrounding medium. The results of this experiment, which are in agreement with those obtained using more traditional “point” sampling and laboratory analysis, are presented along with the strengths and limitations of the thermal-response method of detecting moisture.     

Physicochemical properties and mineral contents of seven different date fruit (Phoenix dactylifera L.) varieties growing from Saudi Arabia

The date (Phoenix dactylifera L.) fruits (Soukari, Soulag, Barhi, Khulas, Rozaiz, Soughi and Monaif) were evaluated with respect to some physical and chemical properties. While crude protein contents of fruits change between 1.51 % (Soulag) to 2.41 % (Soughi), crude fibre contents ranged between 1.91 % (Soukari) to 3.90 % (Barhi). Vitamin C contents of date samples changed between 971.82 mg/kg (Soughi) to 1,453.15 mg/kg (Barhi). Antioxidant activity of date fruits ranged from 80.07 IC₅₀ (Soukari) to 81.21 IC₅₀ (Soulag). The highest phenolic content was found in Khulas with a mean value of 198 mg GAE/100 g. Energy values of date fruits ranged from 3,725 kcal/kg (Soulag) to 3,870 kcal/kg (Soukari). Sucrose contents of date fruits changed between 1.02 % (Soulag) to 55.71 % (Soukari). Mineral contents of several date fruits were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). Date samples contain potassium at a range between 7,468 mg/kg (Khulas) to 9,619 mg/kg (Soulag). Phosphorus contents of fruits were found between 1,848 mg/kg (Soulag) to 3,066 mg/kg (Rozaiz) and followed by magnesium and calcium. The highest Zn (9.33 mg/kg), Cu (4.27 mg/kg) and Mn (3.26 mg/kg) were found in Rozaiz, Soukari and Barhi samples, respectively.