Experimental octanol/water partition coefficients of chlorinated paraffins

Octanol/water partition coefficients (K_OW) of chlorinated paraffins (CPs) from a commercial mixture (‘Cereclor 60L’) were determined using a “slow-stirring” method. Log K_OW values for the different congener groups ranged from 5.85 to 7.14. Equilibrium was reached within a few days, and K_OW values were the same at two CP-concentrations. A clear relationship is found between the total number of chlorine and carbon atoms and log K_OW for the CP-congener groups and a series of smaller chlorinated alkanes from the literature.     

Numerical Simulation of the Thermal Destruction of Some Chlorinated C1 and C2 Hydrocarbons

We have numerically modeled the breakdown of small quantities of several chlorinated hydrocarbons (CH₃CI, CH₂CI₂, CHCI₃, CCI₄, C₂H₃CI, and C₂H₅CI) in a lean mixture of combustion products between 800 and 1480 K. This simulates the fate of poorly atomized waste in a liquid-Injection Incinerator. Kinetics calculations were performed using the CHEMKIN and SENKIN programs, with a reaction mechanism that was developed at Louisiana State University to model flat-flame burner experiments.

A 99.99-percent destruction efficiency was attained In one second at temperatures ranging from 1280 to 960 K, with CCI4 requiring the highest temperature for destruction and C₂H₅CI the lowest. For all compounds except C₂H₅CI, there was a range of temperatures at which byproducts accounted for several percent of the elemental chlorine at the outlet. The more heavily chlorinated compounds formed more byproducts even though the amount of elemental chlorine was the same in all cases. The sensitivity of results to residence time, equivalence ratio, temperature profile, and the presence of additional chlorine, was examined for the case of CHCI₃.     

Decomposition of 2,2',4,4',5,5'-hexachlorobiphenyl with iron supported on an activated carbon from an ion-exchange resin

An activated carbon (AC) containing a high concentration (374 mg g⁻¹) of Fe was prepared by carbonization of an ion-exchange resin. To examine its chemical reactivity as a catalyst to decompose 2,2′,4,4′,5,5′-hexachlorobiphenyl (PCB-153), the decomposition parameters of temperature and time were varied under air or N₂. Decomposition at 350 °C was achieved within 15 min under air and 30 min under N₂, and the efficiency of PCB-153 decomposition was 99.7% and 98.0%, respectively. An analysis of inorganic chloride ions revealed that PCB-153 was mineralized effectively during the decomposition. The Brunauer-Emmett-Teller (BET) surface area and pore volume of the AC were measured to assess the adsorption capacity before and after the decomposition. The differences between decomposition under air and N₂ reflected the differences in the BET surface and pore volume measurements. A decomposition pathway was postulated, and the reactive characteristics of chlorine atoms loaded on the benzene rings followed the order of para > meta > ortho, which agrees with the calculated results from a density functional theory study.     

The aging process of naturally emitted aerosol (sea-salt and mineral aerosol) during long range transport

The aging processes of two representative natural aerosol, sea-salt and mineral aerosol, are investigated by using a box model equipped with a thermodynamic module (SCAPE). The model is shown to successfully describe the aging processes between the gas-phase anthropogenic pollutants (SO₂, NO_x, and NH₃) and primary aerosol particles, including self-neutralization process/chlorine depletion in the sea-salt aerosol; formation/dissipation of carbonate and bicarbonate ions in the mineral aerosol; irreversible dynamic deposition of SO₂ and H₂SO₄; and reversible thermodynamic distribution of inorganic volatile species. It is found that SO₂ and H₂SO₄ tend to deposit onto the mode with the largest surface area, and that ammonia deposition is controlled by preceding SO₂/H₂SO₄ deposition. During the SO₂/H₂SO₄ deposition, chloride and carbonate are continuously released from the sea-salt and mineral dust particles, respectively. The findings by the model predictions are consistent with field and observational studies.     

Atmospheric Chemistry of Toxic Contaminants. 5. Unsaturated Halogenated Aliphatics: Allyl Chloride,Chloroprene, Hexachlorocyclopentadiene,Vinylidene Chloride

Detailed mechanisms are outlined for the chemical reactions involved In the atmospheric removal of four unsaturated chlorinated aliphatic contaminants, allyl chloride, chloroprene, hexachlorocyclopentadiene and vlnylldene chloride. Rate constants estimated from structure-reactivity relationships Indicate rapid removal for all four compounds by reactions with OH (major), ozone, and NO₃, with half-lives of 2-16 hrs for removal by reaction with OH. Reaction products of allyl chloride (formaldehyde, chloroacetaldehyde, peroxychloroacetyl nitrate) and vinylidene chloride (formaldehyde, phosgene, chloroacetyl chloride) are consistent with OH addition-Initiated pathways that include Cl atom elimination. The chlorine atoms produced In the OH reaction sequence react rapidly with all four unsaturated compounds, but these reactions are of negligible Importance for atmospheric removal of the four toxic contaminants studied. Analogous mechanisms are discussed for chloroprene (leading to formaldehyde, CH₂ = CCICHO, and CICOCHO) and for hexachlorocyclopentadlene (leading to oxalyl chloride and CICOCCI₂COCI).     

Influence of Operating Conditions on the Formation of Heavy Metal Compounds During Incineration

ABSTRACT

The formation of Cr, Pb, and Cd species under various operating conditions in a pilot-scale fluidized-bed incinerator was investigated. Examined were the effects of (1) an organic chloride (PVC) additive, (2) an inorganic chloride (NaCl) additive, and (3) NaNO₃ and PVC additives,

under various operating temperatures. Two-stage modeling was performed to match the actual incineration conditions of the current study.

Thermodynamic equilibrium analysis indicated that Cr₂O₃, PbCl₂, and CdCl₂ were the dominant species of Cr, Pb, and Cd when an organic chloride (PVC) was present, whereas PbO and CdO were the dominant species under the other operating conditions. The XRD analysis identified Cr₂O₃, PbCl₂, and CdCl₂»H₂O as the dominant species of Cr, Pb, and Cd when an organic chloride (PVC) was present, whereas Cr₂O₃, PbO, Pb₂O₃, CdO, and CdCO₃ were identified under the other operating conditions. The sodium contained in the feedstock was shown to react with chlorine to form sodium chloride both in modeling results and by X-ray diffraction (XRD) analysis. The temperature of the operating conditions had little effect on the formation of heavy metal species.     

Investigation of a Mercury Speciation Technique for Flue Gas Desulfurization Materials

Abstract

Most of the synthetic gypsum generated from wet flue gas desulfurization (FGD) scrubbers is currently being used for wallboard production. Because oxidized mercury is readily captured by the wet FGD scrubber, and coal-fired power plants equipped with wet scrubbers desire to benefit from the partial mercury control that these systems provide, some mercury is likely to be bound in with the FGD gypsum and wallboard. In this study, the feasibility of identifying mercury species in the FGD gypsum and wallboard samples was investigated using a large sample size thermal desorption method. Potential candidates of pure mercury standards including mercuric chloride (HgCl₂), mercurous chloride (Hg₂Cl₂), mercury oxide (HgO), mercury sulfide (HgS), and mercuric sulfate (HgSO₄) were analyzed to compare their results with those obtained from FGD gypsum and dry wallboard samples. Although any of the thermal evolutionary curves obtained from these pure mercury standards did not exactly match with those of the FGD gypsum and wallboard samples, it was identified that Hg₂Cl₂ and HgCl₂ could be candidates. An additional chlorine analysis from the gypsum and wallboard samples indicated that the chlorine concentrations were approximately 2 orders of magnitude higher than the mercury concentrations, suggesting possible chlorine association with mercury.     

Hg Reactions in the Presence of Chlorine Species: Homogeneous Gas Phase and Heterogeneous Gas-Solid Phase

Abstract

The kinetics of Hg chlorination (with HCl) was studied using a flow reactor system with an online Hg analyzer, and speciation sampling using a set of impingers. Kinetic parameters, such as reaction order (α), overall rate constant (k′ ), and activation energy (E _a), were estimated based on the simple overall reaction pathway. The reaction order with respect to C _Hg, k′, and E _a were found to be 1.55, 5.07 x 10^-2exp(-1939.68/T) [(μg/m³)^-0.55(s)^-1], and 16.13 [kJ/mol], respectively. The effect of chlorine species (HCl, CH₂Cl₂) on the in situ Hg capture method previously de-veloped²⁸ was also investigated. The efficiency of capture of Hg by this in situ method was higher than 98% in the presence of chlorine species. Furthermore, under certain conditions, the presence of chlorine enhanced the removal of elemental Hg by additional gas-phase oxidation.     

Effect of inorganic and organic solutes on zero-valent aluminum-activated hydrogen peroxide and persulfate oxidation of bisphenol A

The effect of varying inorganic (chloride, nitrate, sulfate, and phosphate) and organic (represented by humic acid) solutes on the removal of aqueous micropollutant bisphenol A (BPA; 8.8 μM; 2 mg/L) with the oxidizing agents hydrogen peroxide (HP; 0.25 mM) and persulfate (PS; 0.25 mM) activated using zero-valent aluminum (ZVA) nanoparticles (1 g/L) was investigated at a pH of 3. In the absence of the solutes, the PS/ZVA treatment system was superior to the HP/ZVA system in terms of BPA removal rates and kinetics. Further, the HP/ZVA process was not affected by nitrate (50 mg/L) addition, whereas chloride (250 mg/L) exhibited no effect on the PS/ZVA process. The negative effect of inorganic anions on BPA removal generally speaking increased with increasing charge in the following order: NO₃^? (no inhibition)?<?Cl^? (250 mg/L)?=?SO₄^2??<?PO₄^3? for HP/ZVA and Cl^? (250 mg/L; no inhibition)?<?NO₃^??<?SO₄^2??<?PO₄^3? for PS/ZVA. Upon addition of 20 mg/L humic acid representing natural organic matter, BPA removals decreased from 72 and 100% in the absence of solutes to 24 and 57% for HP/ZVA and PS/ZVA treatments, respectively. The solute mixture containing all inorganic and organic solutes together partly suppressed the inhibitory effects of phosphate and humic acid on BPA removals decreasing to 46 and 43% after HP/ZVA and PS/ZVA treatments, respectively. Dissolved organic carbon removals were obtained in the range of 30 and 47% (the HP/ZVA process), as well as 47 and 57% (the PS/ZVA process) for the experiments in the presence of 20 mg/L humic acid and solute mixture, respectively. The relative Vibrio fischeri photoluminescence inhibition decreased particularly for the PS/ZVA treatment system, which exhibited a higher treatment performance than the HP/ZVA treatment system.     

Tissue distribution and excretion of hexabromobenzene (HBB) and hexachlorobenzene (HCB) administered to rats

Tissue distribution and excretion of hexabromobenzene (HBB) and hexachlorobenzene (HCB) were studied in Wister male rats, after oral administration of these chemicals.There was no difference in the amount of two chemicals excreted in feces for seven days. Their absorption rates through intestine were the same. HBB and HCB also were excreted in urine, but their amounts were very low. Therefore, both chemicals seem to be mainly excreted via feces. HBB and HCB were found to be transported rapidly to all tissues, but the concentrations of HCB were higher than those of HBB in all tissues, indicating the rapid metabolism of HBB. This might be due to the lower bonding energy between bromine and carbon atoms (C₆H₆-Br: 71kcal/mol) compared to that of chlorine and carbon atoms (C₆H₆Cl: 86kcal/mol). The half-lives were 0.7 (phase I) and 48 days (phase II) for HBB and 20 days for HCB in whole body. It is noteworthy that the half-life of HBB at phase II is longer than that of HCB.     

Studies on the Coupling Product between Oxidation Products Derived from Pentachlorophenol and Cyclodextrins

The coupling products (CPs), which were formed via the peroxosulfate catalyzed oxidation of pentachlorophenol (PCP) with iron(III)-tetrakis(sulfonatophenyl)porphyrin (Fe(III)-TPPS) in the presence of hydroxypropyl-β -cyclodextrin (HP-β -CD) or HP-γ -CD, were separated by ultrafiltration from the reaction mixture. When the percentages of chlorine species in the reaction mixture were calculated from the concentrations of organic chlorine in the reaction mixture and CPs, 10–25% of chlorine species in the reaction mixture was organic chlorine that was incorporated into CDs. Analyses of the CPs by pyrolysis-GC/MS (Py-GC/MS) and ¹³C NMR showed that the PCP-derived products were covalently incorporated into the CDs. To evaluate the acute toxicity of the CPs, a Microtox® test was examined. Toxicities of the CPs were reduced slightly, compared to the controls (PCP alone and PCP + reaction blanks). In the reaction blanks, mesaconic acid (MA) moieties were detected as a result of the oxidation of CDs in the absence of PCP. Thus, factors in the toxicities, detected in the CPs, can be attributed to the oxidation products derived from CDs, such as MA, as well as the PCP-derived products incorporated into the CDs.     

A DFT study of the reactions of O3 with Hg° or Br

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole (Farman et al., 1985) and of the ozone depletion events in the polar boundary layer (Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation (Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br₂, the precursor of two Br atoms, via the multiphasic reaction (1):

(1)

HOBr + Br⁻ + H⁺ → H₂O + Br₂

The production of reactive HOBr could occur with the oxidation of BrO by HO₂.     

Modeling heterogeneous ClNO2 formation,chloride availability,and chlorine cycling in Southeast Texas

Nitryl Chloride (ClNO₂) mixing ratios above 1 ppbv have been measured off the coast of Southeast Texas. ClNO₂ formation, the result of heterogeneous N₂O₅ uptake on chloride-containing aerosols, has a significant impact on oxidant formation for the Houston area. This work reports on the modeling of ClNO₂ formation and describes the sensitivity of ClNO₂ formation to key parameters. Model sensitivity analyses found that: (1) Chloride availability limits the formation of nitryl chloride at ground level but not aloft; (2) When excess particulate chloride was assumed to be present at ground level through sea salt, ClNO₂ concentrations increased in some locations by a factor of 13, as compared to cases where sea salt chloride was assumed to be limited; (3) Inland formation of ClNO₂ seems feasible based on chloride availability and could have a large impact on total ClNO₂ formed in the region; and (4) ClNO₂ formation is quite sensitive to the assumed yield of ClNO₂ from N₂O₅ uptake. These results demonstrate that there is a need for further field studies to better understand the geographic extent of ClNO₂ formation and the atmospheric conditions which control partitioning of chloride into the particle phase. In addition, this work examined the role of ClNO₂ in the cycling of chlorine between chloride and reactive chlorine radicals. The modeling indicated that the majority of reactive chlorine in Texas along the Gulf coast is cycled through ClNO₂, demonstrating the importance of including ClNO₂ into photochemical models for this region.     

Inorganic Acid Emission Factors of Semiconductor Manufacturing Processes

Abstract

A huge amount of inorganic acids can be produced and emitted with waste gases from integrated circuit manufacturing processes such as cleaning and etching. Emission of inorganic acids from selected semiconductor factories was measured in this study. The sampling of the inorganic acids was based on the porous metal denuders, and samples were then analyzed by ion chromatography. The amount of chemical usage was adopted from the data that were reported to the Environmental Protection Bureau in Hsin-chu County according to the Taiwan Environmental Protection Agency regulation. The emission factor is defined as the emission rate (kg/month) divided by the amount of chemical usage (L/month). Emission factors of three inorganic acids (i.e., hydrofluoric acid [HF], hydrochloric acid [HQ], and sulfuric acid [H₂SO₄]) were estimated by the same method. The emission factors of HF and HCl were determined to be 0.0075 kg/L (coefficient of variation [CV] = 60.7%, n = 80) and 0.0096 kg/L (CV = 68.2%, n = 91), respectively. Linear regression equations are proposed to fit the data with correlation coefficient square (R²) = 0.82 and 0.9, respectively. The emission factor of H₂SO₄, which is in the droplet form, was determined to be 0.0016 kg/L (CV = 99.2%, n = 107), and its R² was 0.84. The emission profiles of gaseous inorganic acids show that HF is the dominant chemical in most of the fabricators.     

Comparison of various advanced oxidation processes for the degradation of phenylurea herbicides

Various types of advanced oxidation processes (AOPs), such as UV photolysis, ozonation, heterogeneous photocatalysis and their combinations were comparatively examined at the same energy input in a home-made reactor. The oxidative transformations of the phenylurea herbicides fenuron, monuron and diuron were investigated. The initial rates of transformation demonstrated that UV photolysis was highly efficient in the cases of diuron and monuron. Ozonation proved to be much more effective in the transformation of fenuron than in those of the chlorine containing monuron and diuron. In heterogeneous photocatalysis, the rate of decomposition decreased with increase of the number of chlorine atoms in the target molecule. Addition of ozone to UV-irradiated solutions and/or TiO₂-containing suspensions markedly increased the initial rates of degradation. Dehalogenation of monuron and diuron showed that each of these procedures is suitable for the simultaneous removal of chlorinated pesticides and their chlorinated intermediates. Heterogeneous photocatalysis was found to be effective in the mineralization.     

The internal barriers of rotation for the 209 polychlorinated biphenyls

The internal barrier of rotation (Erot) was calculated for all 209 polychlorinated biphenyls (PCBs) by using a semi-empirical method, viz. the Austin Model 1 (AMI) Hamiltonian. The difference in total energy between a forced planar state and an optimised twisted structure was defined as Erot. The Erot values were in the range of 8.33 to 483 kj/mol, and were significantly influenced by the number of chlorine atoms inortho position. An additional structural characteristic of the PCBs influencing Erot ofortho substituted congeners was substitution by chlorine atoms in vicinalmeta positions, which is assumed to prevent outward bending ofortho substituents. This so-called buttressing effect contributed with 4 to 31 kj/mol per added chlorine atom. In conclusion, the internal barrier of rotation, calculated for all 209 PCBs, provides an important structure dependent physico-chemical parameter for multivariate modelling of future quantitative structure-activity and structure-property relationships (QSARs/QSPRs).     

Atmospheric fate of acrylic acid and acrylonitrile: Rate constants with Cl atoms and OH radicals in the gas phase

Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with acrylic acid and acrylonitrile have been determined at 298 K and atmospheric pressure. The decay of the organics was followed using a gas chromatograph with a flame ionization detector (GC-FID) and the rate constants were determined using a relative rate method with different reference compounds. Room temperature rate constants are found to be (in cm³ molecule⁻¹ s⁻¹): k₁(OH+CH₂CHC(O)OH)=(1.75±0.47)×10⁻¹¹, k₂(Cl+CH₂CHC(O)OH)=(3.99±0.84)×10⁻¹⁰, k₃(OH+CH₂CHCN)=(1.11±0.33)×10⁻¹¹ and k₄(Cl+CH₂CHCN)=(1.11±0.23)×10⁻¹⁰ with uncertainties representing ±2σ. This is the first kinetic study for these reactions under atmospheric pressure. The rate coefficients are compared with previous determinations taking into account the effect of pressure on the rate constants. The effect of substituent atoms or groups on the overall rate constants is analyzed in comparison with other unsaturated compounds in the literature. In addition, atmospheric lifetimes based on the homogeneous sinks of acrylic acid and acrylonitrile are estimated and compared with other tropospheric sinks for these compounds.     

Primary product distribution from the Cl-atom initiated atmospheric degradation of furan: Environmental implications

Furan is an aromatic hydrocarbon present in both urban and rural atmospheres, which is emitted mainly by biomass burning and the combustion of fossil fuel. Reaction of furan and Cl atoms may be important in areas where chlorine atom concentrations are potentially high such as marine and coastal regions or continental atmospheres where industrial activity emits molecular chlorine or photo-labile Cl-containing compounds. To assess the importance of this reaction and to investigate whether any unique chlorine-containing product is formed the products of the reaction of Cl atoms with furan have been determined under atmospheric conditions. For the study two different sampling/detection methods have been used: (1) Solid-Phase MicroExtraction, with subsequent analysis by thermal desorption, and gas chromatography with mass spectrometry or flame ionization detection (SPME/GC-MS/FID), and 2-“in situ” with long path fourier transform infrared spectroscopy (FTIR). The yields of primary reaction products in the absence of NO were: 5-chloro-2(5H)-furanone (64.5±10.7)%, E-butenedial (11±3)%, 5-hydroxy-2(5H)-furanone (⩽2.4%) and Z-butenedial (1.6±0.5)%. Other products generated by secondary reactions were 2(3H)-furanone (2.8±1.9)%, HCl (21.1±3%) and CO. Maleic anhydride was detected with a yield of about 2%, however, this yield may be a combination of both primary and secondary reactions. All errors are ±2σ. The observed products confirm that addition of Cl atoms to the double bond of furan is the dominant reaction pathway.     

Mechanochemical destruction of mirex co-ground with iron and quartz in a planetary ball mill

Mechanochemical destruction (MCD) has been recognized as a promising non-combustion technology for the disposal of obsolete pesticides belonging to the persistent organic pollutants (POPs). Mirex, a termiticide ever used for many years in China, was ball milled in the presence of various reagent(s) in a planetary ball mill at room temperature to investigate the destruction efficiency. The ground samples were characterized and analyzed by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, gas chromatography (GC), and ion chromatography (Martins, Bicego et al.). Under the same conditions of mill rotary rate and charge ratio, the mixture of iron powder and quartz sand (Fe/SiO₂) was found best in promoting the mirex destruction. Mirex was completed destroyed after 2 h grinding at a charge ratio of 36:1 (reagent/mirex, m/m) and a mill rotation speed of 550 rpm. No organic compound was detected by GC/μECD screening. The yield of water-soluble chlorine determined by ion chromatography (Martins, Bicego et al.) in the final residue accounted for 90.7% of chlorine in the original mirex, which indicated a nearly complete dechlorination. Signals of both graphite and amorphous carbon were found in the Raman spectra of the co-ground powder samples. With the main final degradation products of water soluble Cl and carbon, the mechanism of the mechanochemical destruction approach should be dechlorination followed by the carbonization.