Organophosphate flame retardants and plasticisers in wastewater treatment plants

Previous studies have revealed that chlorinated and non-chlorinated organophosphorous flame retardants and plasticisers are important contaminants in German surface waters and it has been demonstrated that wastewater treatment plants contribute to the emission of these substances. In this study temporal development as well as elimination efficiency were determined in two wastewater treatment plants (STP) in the Ruhr/Rhine area at different stages of the wastewater treatment process. The samples were analysed for the non-chlorinated organophosphate esters tri-n-butylphosphate (TnBP), tri-iso-butylphosphate (TiBP), tris-(butoxyethyl)-phosphate (TBEP) and triphenylphosphate (TPP) and the chlorinated organophosphate esters tris-(2-chloro, 1-methylethyl)-phosphate (TCPP), tris-(2-chloro-, 1-chloromethylethyl)-phosphate (TDCP) and tris-(2-chloroethyl)-phosphate (TCEP). The study showed that there were significant differences in the elimination of chlorinated and non-chlorinated organophosphorous flame retardants. The elimination rates ranged from 57-86% for TiBP, TnBP and TBEP at both STP's. No elimination of the chlorinated flame retardants TCPP, TDCP and TCEP was observed in any of the sampled STPs. At both STPs the first treatment steps and the final filtration did not contribute to the elimination of the non-chlorinated organophosphorous flame retardants while the aeration step did. At both STPs the efficiency of the cleaning process concerning the flame retardants was comparable. Thus the type of construction of the STP was not relevant for the elimination of these substances. Additionally a strong day-to-day variation was observed, while in one STP a temporal trend for TCPP during the week was found.     

Quantitative PCR analysis of house dust can reveal abnormal mold conditions

Indoor mold concentrations were measured in the dust of moldy homes (MH) and reference homes (RH) by quantitative PCR (QPCR) assays for 82 species or related groups of species (assay groups). About 70% of the species and groups were never or only rarely detected. The ratios (MH geometric mean : RH geometric mean) for 6 commonly detected species (Aspergillus ochraceus, A. penicillioides, A. unguis, A. versicolor, Eurotium group, and Cladosporium sphaerospermum) were >1 (Group I). Logistic regression analysis of the sum of the logs of the concentrations of Group I species resulted in a 95% probability for separating MH from RH. These results suggest that it may be possible to evaluate whether a home has an abnormal mold condition by quantifying a limited number of mold species in a dust sample. Also, four common species of Aspergillus were quantified by standard culturing procedures and their concentrations compared to QPCR results. Culturing underestimated the concentrations of these four species by 2 to 3 orders of magnitude compared to QPCR.     

Development and validation of methods for environmental monitoring of cyclophosphamide in workplaces

Methods to monitor contamination of workplaces with antineoplastic drugs have been developed and validated. Cyclophosphamide (CP) was used as a model compound as it is one of the most commonly used antineoplastic drugs. A wipe sampling method to detect contamination with CP at surfaces was developed. A personal air sampling method to sample gas and vapour on solid sorbent tubes and particles with filters was also developed. Wipe and filter samples were extracted and sorbent samples were eluted, all with ethyl acetate. The samples were analysed with liquid chromatography tandem mass spectrometry. (2)H(6)-labelled cyclophosphamide was used as an internal standard. The between-day precision was 2-5% for wipe samples, 4-6% for sorbent samples and 3-8% for filter samples. The limit of detection was 0.02 ng CP per sample for the wipe and filter methods and 0.03 ng CP per sample for the solid sorbent method. Wipe sampling on surfaces made of different materials resulted in mean recoveries between 78-106%. The desorption recovery was between 97-102% for the wipe samples, 97% for the sorbent samples and 101% for the filter samples. Samples were stable for up to 2 months at 5 degrees C and -20 degrees C and for about 2 d at room temperature. The developed methods were applied to the measurement of contamination with CP in a hospital pharmacy. Trace amounts of CP, 1.3 and 1.4 ng, were detected on surfaces in the pharmacy.     

Trihalomethanes in Drinking Water of Greater Québec Region (Canada): Occurrence, Variations and Modelling

The levels of trihalomethanes (THMs) – the main species of by-product from water chlorination – were monitored in thedistribution systems of the five major drinking water utilitiesof the greater area of Québec City in order to investigate andmodel their occurrence on a spatial and seasonal basis. Data forTHMs and other water quality and operational parametersassociated with their formation were generated through a 16 monthsampling program involving several sites representing variablewater residence times, from the plant to the system extremity.The results demonstrate that the differences in measured THMlevels between the five utilities are mainly due to the variablequality of raw waters, the type of water treatment process beingused and the type and levels of applied disinfectant. Dependingon the utility, average THM levels were from 1.3 to 2.5 timeshigher in the system extremities than in the water leaving thetreatment plant. Also, average levels of THMs measured in summerat the distribution system extremities were, depending on theutility, from 2.5 to 5 times higher than the average levelsmeasured in winter. The seasonal differences were found to besignificantly greater than those observed by others in waterutilities in the United States and Europe and are explained inlarge part by the considerable changes, over the year, in thequality and temperature of surface waters in Southern Québec. Forthe five utilities under study, multivariate regression modelswere developed in order to predict spatial and seasonalvariations of THMs. Both residual chlorine demand and temperaturewere found to be better, statistically, as predictors for THMoccurrence. The usefulness of the developed models for routineand long term water quality management, as well as for assessmentof human exposure to THMs, are also discussed.     

Formation and Emission of N2O and CH4 from Compost Heaps of Organic Household Waster

Composting can be a source of N₂O andCH₄ production. In this investigation, differentcompost heaps of organic household waste weremonitored with the focus on potential formation ofCH₄ and N₂O in the heaps and emission ofthese gases from the heaps. The studied compost heapshad different compost ages, turning intervals andcompost sizes. The analysed compost gases containedbetween 1–3421 L of N₂O-N L^-1 and 0–470 mL of CH₄ L^-1. The emission rates ofN₂O and CH₄ from the compost heaps werebetween 1–1464 mg N₂O m^-2 day^-1 and0–119 000 mg CH₄ m^-2 day^-1. These verylarge differences in compost gas composition andemission indicate the importance of compostmanagement. The results also give an understanding ofwhere in the composting process an increasing emissionof N₂O and CH₄ can occur.     

The collection of PM10 for toxicological investigation: comparisons between different collecting devices

A positive correlation has been established between increased levels of airborne particulate pollution and adverse health effects, the toxicological mechanisms of which are poorly understood. For toxicologists to unambiguously determine thesemechanisms, truly representative samples of ambient PM₁₀ are required. This presents problems, as PM₁₀ collecting equipment commonly employed, such as the Tapered Element Oscillating Microbalance (TEOM®), heat the inflow toexclude moisture or use fibrous filters, resulting in a PM₁₀sample that may have undergone significant chemical change on thefilter surface or is contaminated by filter fibres. Other systems(i.e. Negretti and Partisol) can successfully collect PM₁₀ without chemical alteration or filter contamination. Comparativecollections from Port Talbot, S. Wales suggest that TEOMs and Negretti/Partisol systems collect different PM₁₀'s; the principle difference arising from the TEOM's heating chamber, which precipitates water-soluble ions and volatilises some organic components. This results in both the mass and compositionof the PM₁₀'s being altered. Particle size distributionsfor Negretti and Partisol collections highlighted differences mainly attributed to different flow rates. The results of thiswork demonstrate that simple correlations between PM₁₀ massand adverse health effects are problematic. Furthermore, elucidation of the complex fractionation and chemical changes indifferent collectors is necessary.     

On-line solid phase extraction with polyurethane foam: trace level spectrophotometric determination of iron in natural waters and biological materials

This paper reports the development of a simple and accurate on-line procedure for preconcentration and determination of dissolved iron in waters and biological materials using unloaded polyether-type polyurethane foam as solid extractor. In the developed flow injection system, the analyte was preconcentrated from acidic aqueous medium as iron-thiocyanate complex with post-elution with ascorbic acid solution and spectrophotometric measurement with 1,10-phenanthroline as colorimetric reagent. In order to improve the performance of the system several chemical and flow variables were investigated as well as the effect caused by the presence of possible interferents. The method was validated by the analysis of two certified reference materials. Application of the methodology was carried out by the determination of dissolved iron content in eight natural water samples with different characteristics. The results were compared with those obtained by electrothermal atomic absorption spectrometry (ETAAS) and no statistical difference was observed. The detection limit was 0.75 microgram l-1 and the RSD was 1.2% for 2 min preconcentration time. At this condition, a productivity of 20 samples h-1 was achieved. Increasing the preconcentration time up to 3 min, a detection limit of 0.45 microgram l-1, an RSD of 1.5% and an analytical throughput of 15 h-1 were verified.     

Application of intrawell testing of RCRA groundwater monitoring data when no upgradient well exists

A statistical quality control approachto detect changes in groundwater quality from aregulated waste unit is described. The approachapplies the combined Shewhart-CUSUM control chartmethodology for intrawell comparison of analyteconcentrations over time and does not require anupgradient well. A case study from the U.S.Department of Energy's Hanford Site is used forillustration purposes. This method is broadlyapplicable in groundwater monitoring programs wherethere is no clearly defined upgradient location, thegroundwater flow rate is exceptionally slow, or wherea high degree of spatial variability exists inparameter concentrations. This study also indicatesthat the use of the Data Quality Objectives (DQO)process can assist in designing an efficient andcost-effective groundwater monitoring plan to achievethe optimum goal of both low false positive and lowfalse negative rates (high power).     

An Evaluation of Selenium Concentrations in Water, Sediment, Invertebrates, and Fish from the Republican River Basin: 1997–1999

The Republican River Basin of Colorado,Nebraska, and Kansas lies in a valley which contains PierreShale as part of its geological substrata. Selenium is anindigenous constituent in the shale and is readily leached intosurrounding groundwater. The Basin is heavily irrigated throughthe pumping of groundwater, some of which is selenium-contaminated, onto fields in agricultural production. Water,sediment, benthic invertebrates, and/or fish were collected from46 sites in the Basin and were analyzed for selenium to determinethe potential for food-chain bioaccumulation, dietary toxicity,and reproductive effects of selenium in biota. Resultingselenium concentrations were compared to published guidelines orbiological effects thresholds. Water from 38% of the sites (n = 18) contained selenium concentrations exceeding 5 g L^-1, which is reported to be a high hazard for selenium accumulation into the planktonic food chain. An additional 12 sites (26% of the sites) contained selenium in water between 3–5 g L^-1, constituting a moderate hazard. Selenium concentrations in sedimentindicated little to no hazard for selenium accumulation fromsediments into the benthic food chain. Ninety-five percent ofbenthic invertebrates collected exhibited selenium concentrationsexceeding 3 g g^-1, a level reported as potentially lethal to fish and birds that consume them. Seventy-five percent of fish collected in 1997, 90% in 1998, and 64% in 1999 exceeded 4 g g^-1selenium, indicating a high potential for toxicity andreproductive effects. However, examination of weight profilesof various species of collected individual fish suggestedsuccessful recruitment in spite of selenium concentrations thatexceeded published biological effects thresholds for health andreproductive success. This finding suggested that universalapplication of published guidelines for selenium may beinappropriate or at least may need refinement for systems similarto the Republican River Basin. Additional research is needed todetermine the true impact of selenium on fish and wildliferesources in the Basin.     

Measurements of fractionated gaseous mercury concentrations over northwestern and central Europe, 1995-99

Although it makes up only a few per cent. of total gaseous mercury (TGM) in the atmosphere, the fraction of oxidised (divalent) mercury plays a major role in the biogeochemical cycle of mercury due to its high affinity for water and surfaces. Quantitative knowledge of this fraction present in mixing ratios in the parts-per-10(15) (ppq) range is currently very scarce. This work is based on approximately 220 data for divalent gaseous mercury (DGM) collected during 1995-99 in ambient air. Over the course of the measurements, the sampling and analytical methods were modified and improved. This is described here in detail and includes transition from wet leaching and reduction procedures to thermo-reductive desorption, the use of annular as well as tubular denuders and adoption of an automated sampling system. The concentration of DGM exhibited a strong seasonal behaviour in contrast to atomic gaseous mercury, with low values in winter and maximum values in summer. The DGM/TGM ratios were frequently found to be below the detection limit (< or = 1%) and in the range 1-5%. A trend of diurnal DGM patterns was observed and implies photolytically induced sources. Scavenging of DGM during rain events was also noticed.