Rejection of emerging organic micropollutants in nanofiltration-reverse osmosis membrane applications.

The rejection of emerging trace organics by a variety of commercial reverse osmosis (RO), nanofiltration (NF), and ultra-low-pressure RO (ULPRO) membranes was investigated using TFC-HR, NF-90, NF-200, TFC-SR2, and XLE spiral membrane elements (Koch Membrane Systems, Wilmington, Massachusetts) to simulate operational conditions for drinking-water treatment and wastewater reclamation. In general, the presence of effluent organic matter (EfOM) improved the rejection of ionic organics by tight NF and RO membranes, as compared to a type-II water matrix (adjusted by ionic strength and hardness), likely as a result of a decreased negatively charged membrane surface. Rejection of ionic pharmaceutical residues and pesticides exceeded 95% by NF-90, XLE, and TFC-HR membranes and was above 89% for the NF-200 membrane. Hydrophobic nonionic compounds, such as bromoform and chloroform, exhibited a high initial rejection, as a result of both hydrophobic-hydrophobic solute-membrane interactions and steric exclusion, but rejection decreased significantly after 10 hours of operation because of partitioning of solutes through the membranes. This resulted in a partial removal of disinfection byproducts by the RO membrane TFC-HR. In a type-II water matrix, the effect of increasing feed water recoveries on rejection of hydrophilic ionic and nonionic compounds was compound-dependent and not consistent for different membranes. The presence of EfOM, however, could neutralize the effect of hydrodynamic operating condition on rejection performance. The ULPRO and tight NF membranes were operated at lower feed pressure, as compared to the TFC-HR, and provided a product water quality similar to a conventional RO membrane, regarding trace organics of interest.     

Estimation of selected physicochemical properties for methylated naphthalene compounds

Liquid aqueous solubility (S(w,L)), octanol/water partition coefficients (K(ow)), liquid vapor pressure (P(v,L)), and Henry's law constants (H(c)) were estimated for 20 methylated naphthalenes ranging from monomethyl to tetramethylnaphthalenes. Chromatographic methods were used for the estimation. Chromatographic retention measurements were conducted for 11 reference compounds and regressions were fit between the retention indices and the physicochemical properties. HPLC octadecylsilyl column with acetonitrile/water eluent was used for the estimation of S(w,L) and K(ow). Two GC columns, HP5-MS and a more hydrophobic HP-1, were tested for the estimation of P(v,L). Measured retention indices for the methylated naphthalenes were entered to the regression equations to calculate the physicochemical properties for these compounds. Literature values, where available, were used to validate the calculated values. The method accurately estimated the physicochemical properties. Estimated S(w,L) and P(v,L) decreased with the number of methyl groups. K(ow) increased with the number of methyl groups. There was no obvious relation between H(c) and the number of methyl groups. Log S(w,L) ranged from 0.885 for 1,2,5,6-tetramethylnaphthalene to 2.269 for 1-methylnaphthalene (mmol/m(3)). Log K(ow) varied from 3.89 for 1-methylnaphthalene to 4.95 for 1,2,5,6-tetramethylnaphthalene. Log P(v,L) ranged from -0.983 for 1,2,5,6-tetramethylnaphthalene to 0.789 for 2-methylnaphthalene (Pa). Log H(c) varied from 1.03 for 1,4,5-trimethylnaphthalene to 1.73 for 2,6-dimethylnaphthalene (Pa m(3)/mol). There were no apparent effects of GC column hydrophobicity on the accuracy of the results. Estimation of S(w,L) and K(ow) based on GC retention indices was not as accurate as with HPLC. Comparison of the estimated values with values predicted by EPIWIN indicated that EPIWIN is useful in giving order-of-magnitude prediction of physicochemical properties.     

A comparison of polycyclic aromatic hydrocarbon and petroleum hydrocarbon uptake by mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) in Hong Kong coastal waters

The ability of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) to accumulate polycyclic aromatic hydrocarbons (PAHs) and petroleum hydrocarbons (PHCs) from five sites in Hong Kong's coastal waters was compared. Mussels consistently had higher levels of contaminants, but their utility was limited at one highly polluted site due to mortality. Mussels and SPMDs ranked sites differently in terms of individual contaminant levels. Although SPMDs overcome many of the disadvantages of using living organisms to measure contaminants in marine waters, they cannot be used as "mimics" due to different PAH and PHC accumulation patterns.     

Modelling of silica diffusion experiments with Si in Boom Clay

A mathematical model describing the dissolution of nuclear glass directly disposed in clay combines a first-order dissolution rate law with the diffusion of dissolved silica in clay. According to this model, the main parameters describing the long-term dissolution of the glass are ηR, the product of the diffusion accessible porosity η and the retardation factor R, and the apparent diffusion coefficient D_app of dissolved silica in clay.For determining the migration parameters needed for long-term predictions, four Through-Diffusion (T-D) experiments and one percolation test have been performed on undisturbed clay cores. In the Through-Diffusion experiments, the concentration decrease after injection of ³²Si (radioactive labelled silica) was measured in the inlet compartment. At the end of the T-D experiments, the clay cores were cut in thin slices and the activity of labelled silica in each slice was determined. The measured activity profiles for these four clay cores are well reproducible.Since no labelled silica could be detected in the outlet compartments, the Through-Diffusion experiments are fitted by two In-Diffusion models: one model assuming linear and reversible sorption equilibrium and a second model taking into account sorption kinetics. Although the kinetic model provides better fits, due to the sufficiently long duration of the experiments, both models give approximately similar values for the fit parameters. The single percolation test leads to an apparent diffusion coefficient value about two to three times lower than those of the Through-Diffusion tests.Therefore, dissolved silica appears to be strongly retarded in Boom Clay. A retardation factor R between 100 and 300 was determined. The corresponding in situ distribution coefficient K_d is in the range 25–75 cm³ g⁻¹. The apparent diffusion coefficient of dissolved silica in Boom Clay is estimated between 2×10⁻¹³ and 7×10⁻¹³ m² s⁻¹. The pore diffusion coefficient is in the range from 6×10⁻¹¹ to 1×10⁻¹⁰ m² s⁻¹.     

Soviet and post-Soviet environmental management: lessons from a case study on lead pollution

Through a case study on lead pollution in the former Soviet Union, the linkage of policy, environmental science, and environmental management is explored, and compared with the US experience. Soviet bans on leaded gasoline and lead-based paint appear to have been effective. Regional governments, in cooperation with the petroleum industry, are taking the initiative in phasing out leaded gasoline, to some extent in defiance of federal policy. Problems with management of lead-acid batteries have been worsened by the collapse of the political system. Lack of reliable environmental data impedes reliable environmental assessment. The types of environmental measurements reflect an emphasis on multipollutant environmental contamination, rather than on human exposure to single pollutants.     

Monitoring of heavy metal deposition in Northern Italy by moss analysis

A survey of heavy metal deposition in the mountainous territories of Northern Italy was carried out in 1995-96. Moss samples (mainly Hylocomium splendens) were collected in a dense network of sites (about 3.2 sites/1000 km(2)) and the data of metal concentrations in moss tissues were statistically correlated with environmental and climatic factors, as well as with bulk deposition of elements and elemental concentrations in the soil. Three main geographic patterns of metal concentration in mosses could be defined: (1) Fe, Ni, and Cr, all derived both by soil particulates and anthropogenic emissions connected with ferrous metal manufacturing, were mostly concentrated in Northwestern Italy; (2) Cu and Zn, as typical multi-source elements, showed rather high concentrations with little ranges of variation over the whole area and small peaks reflecting local source points; (3) Cd and Pb reflected long-distance transport and showed highest concentrations in the regions with highest precipitation, especially in the Eastern Alps.     

Photodegradation and volatility of pesticides

BACKGROUND AND OBJECTIVES: Among the factors affecting the environmental fate of surface-applied pesticides several biological as well as abiotic factors, such as volatilization and photochemical transformations are of particular interest. Whereas reliable measurement methods and models for estimating direct photodegradation are already available for the compartments of water and atmosphere and individual subprocesses have already been described in detail, there is still a need for further elucidation concerning the key processes of heterogeneous photodegradation of environmental chemicals on surfaces. METHODS: In order to systematically examine the direct and indirect photodegradation of 14C-labeled pesticides on various surfaces and their volatilization behavior, a new laboratory device ('photovolatility chamber') was designed according to US EPA Guideline 161-3. Model experiments under controlled conditions were conducted investigating the impact of different surfaces, i.e. glass, soil dust and radish plants, and environmental factors, i.e. irradiation and atmospheric ozone (O3), on the photodegradation and volatilization of surface-deposited [phenyl-UL-14C]parathion-methyl (PM). RESULTS AND DISCUSSION: Depending on the experimental conditions, parathion-methyl was converted to paraoxon-methyl, 4-nitrophenol, unknown polar products and 14CO2. With respect to the direct photodegradation of PM (experiments without O3), the major products were polar compounds and 14CO2, due to the rapid photochemical mineralization of 4-nitrophenol to 14CO2. Paraoxon-methyl and 4-nitrophenol formation was mainly mediated by the combination of light, O3, and *OH radicals. In radish experiments PM photodegradation was presumably located in the cuticle compartment, which exhibited a sensitized photodegradation, as more unknown products were yielded compared to the glass and soil dust experiments. This could be explained by intensifying the inherent PM degradation in the dark with the same product spectrum. Due to photochemical product formation, which is an antagonistic process to the volatilization of parent compound, the volatilization of unaltered parathion-methyl from each surface generally decreased in the presence of light, particularly in combination with increasing O3 concentrations and *OH radical production rates. CONCLUSION: First results demonstrated that the photovolatility chamber provides a special tool for the systematic evaluation of (a) photodegradation of surface-located pesticide residues, i.e. measuring qualitative aspects of direct and indirect photodegradation together with relative photodegradation rates, and (b) volatilization of pesticides on surfaces by including and optionally varying relevant parameters such as light, atmospheric O3 concentration, surface temperature, air temperature, air flow rate. OUTLOOK: The experimental facility represents an important complement to lysimeter and field studies, in particular for experiments on the volatilization of pesticides using the wind tunnel system. With the photovolatility chamber special experiments on photodegradation, volatilization and plant uptake can be conducted to study key processes in more detail and this will lead to a better understanding of the effects of certain environmental processes on the fate of released agrochemicals contributing to an improved risk assessment.     

Use and validation of novel snow samplers for hydrophobic, semi-volatile organic compounds (SVOCs)

Two novel gas-tight snow samplers (snow-can and snow-tube) are presented and the performance of the snow-can in a field trial was assessed. The methodology for the sampling, extraction and analysis of persistent organic pollutants (POPs) are detailed. These samplers allow the various components of a snow sample to be analysed separately; these included the meltwater (MW), particulate matter (GFF) and vapour in the headspace (HS). Snow samples collected on the Punta Indren glacier in the Italian Alps revealed the occurrence of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OC). Replicate samples of the same snow type were undertaken as a test of sampling precision. Relative standard deviations (RSDs) for SigmaPCBs and SigmaPAHs were approximately 30% and approximately 35% respectively. The lowest precision was found for the particle-laden snow, notably for the heavier PCB homologues. For the chlorinated compounds, the pesticides lindane and endosulfan-I had the highest levels in snow, with mean concentrations of 402 and 103 pgl(-1) (snow meltwater) respectively. The vapour present in the headspace (HS) comprised a minor component of a collected sample for all compounds, but HS concentrations for three lighter PAHs gave good agreement with those calculated based on their dimensionless Henry's law constants. This suggests that volatilisation during melting of aged snow-can be reasonably predicted with knowledge of the temperature-dependent Henry's law constant.     

Accumulation and tissue distribution of selected polychlorinated biphenyl congeners in chickens

During one to three consecutive periods of 2 weeks, broiler chickens (n = 108) received test dies to which different amount of PCBs (7 congeners) were added. The relationship between exposure time and accumulation of individual congeners in different chicken tissues, such as breast, thigh and abdominal fat tissue, was observed. In all tissues, the vast majority of the PCB accumulation occurred during the first 2 weeks of exposures. After that, PCB concentrations only increased in the abdominal fat tissue of the animals. The individual PCBs were distributed differently in the various tissues. While CBs 28, 118, 138, 153 and 180 accumulated in the chickens, CBs 52 and 101 were metabolized, but no methyl sulphone metabolites of these congeners could be detected. Our results provide information on the absorption, tissue distribution and biotransformation of the individual PCB congeners and confirm the structure-activity relationships for metabolism of PCBs in birds, which are different from those in fish or mammalian species.     

Levels and profiles of PCDDs,PCDFs and cPCBs in Belgian breast milk. Estimation of infant intake

Congener-specific analyses of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and non-ortho (coplanar) polychlorinated biphenyls (cPCBs) were performed on 20 non-pooled breast milk samples collected in or close to an industrial area of Wallonia (Belgium). PCDD/F concentrations ranged between 16.0 and 52.1 pg TEQ/g fat, with a mean value of 29.4 pg TEQ/g fat. If coplanar PCBs (77, 126, 169) are included in TEQ calculations, levels ranged between 22.2 and 100.2 pg TEQ/g fat, with a mean value of 40.8 pg TEQ/g fat. It appears that 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and PCB-126 account for more than 90% of the TEQ. Estimated PCDD/F dietary intake is 76 pg TEQ/kg body weight (bw)/day. This value is almost 20 times higher than the World Health Organization tolerable daily intake. A value of 103 pg TEQ/kg bw/day represents the intake of PCDDs, PCDFs and cPCBs (no mono-ortho PCBs included).