Comparison of haloacetic acids in the environment of the Northern and Southern Hemispheres

Haloacetic acids (HAAs) are a family of compounds whose environmental concentrations have been extensively studied, primarily in Europe. Depending on the compound, their sources are believed to be both natural and anthropogenic. To better understand possible sources and contribute to the knowledge of the global distribution of these compounds, especially between the Northern and Southern Hemispheres, samples of precipitation, soils, and conifer needles were collected from Canada, Malawi, Chile, and the U.K. Precipitation samples exhibited highest HAA concentrations in collections from Canada, and lowest in those from Malawi. Malawi samples contained measurable levels of monobromoacetic acid (MBA) (56 ng/ L) unlike those from most other locations (< 9 ng/L). Soil HAA concentration levels were highest in the U.K. (e.g., 7.3 ng/g average TCA) and lowest in Malawi (0.8 ng/g average TCA), with Chile having higher levels (4.8 ng/g average TCA) than Canada (3 ng/g average TCA). Malawi soils contained small amounts of MBA (2 ng/g), in common with the two most southern of the 11 Chilean sites. Analysis of soil cores (10-cm depth sliced at 1 cm) from sites in Malawi and Chile showed that trichloroacetic acid (TCA) generally declined with depth while mono- and dichloroacetic acid (MCA and DCA) showed no trend. MCA, DCA, and TCA concentrations in archived U.K. soil samples increased by factors of 2, 4, and 5-fold over 75 years while TFA showed no consistent trend. Monochloroacetic acid (MCA) was detected in pine needles collected from Malawi. U.K. needle samples had the highest concentrations of all chloroacetic acids (CAAs): MCA, 2-18 ng/g; dichloroacetic acid (DCA), 2-38 ng/g; and trichloroacetic acid (TCA), 28-190 ng/g. Conifer needles from Canada and Chile contained CAAs at levels ranging from < 2 to 16 ng/g wet wt. Trifluoroacetic acid concentrations generally declined with increasing elevation in the samples from the Rocky Mountains in western Canada. The results indicate that concentrations of HAAs are greatest in the industrialized Northern Hemisphere but there are significant amounts of these compounds in the less industrialized Southern Hemisphere.     

Distribution of haloacetic acids in the water columns of the Laurentian Great Lakes and Lake Malawi

Haloacetic acids (HAAs) are persistent and mildly phytotoxic compounds that have been detected in many aquatic environments, including the waters of the Great Lakes. Sources of HAAs, especially of trifluoroacetic acid (TFA), are not well understood. In this study we assessed the influence of urbanization on the concentrations and profiles of HAAs in the Laurentian Great Lakes and in Lake Malawi, an African Great Lake. Vertical depth profiles for these compounds were taken for each of the Great Lakes with additional profiles taken 2 years later for Lakes Erie and Ontario. The results showed that while TFA was relatively constant throughout the water column, the chloroacetic acids (CAAs) varied with depth. There was a trend of increasing TFA proceeding from Lake Superior to Lake Ontario (18-150 ng/L). Total CAA concentrations were relatively constant throughout the lakes (approximately 500 ng/L) with dichloroacetic acid being the most abundant. No bromoacetic acids were detected. In the Detroit River, a connecting channel between Lakes Huron and Erie, the TFA values were similar to those in Lake Huron, but the CAAs levels were higher than in the upstream lakes and dependent on location, indicating inputs from urban areas along the river. These results were compared to those from Lake Malawi, which has a high population density within the watershed but no heavy industry. CAAs were nondetectable, and TFA concentrations were just at the detection limit (1 ng/L). Total HAA in the water column of Lakes Superior and Huron was compared to annual precipitation inputs at a site situated near both lakes. For Lake Huron, precipitation was a minor contributor to the total HAA inventory of the lake, but for Lake Superior precipitation could be the major contributor to the mass of HAA in this lake. Generally, high HAA levels paralleled the degree of industrial activity in the adjacent waters.     

Haloacetates in fog and rain

Atmospheric haloacetates can arise from photochemical degradation of halogenated hydrocarbons and from direct anthropogenic emissions. Furthermore, there is also evidence of natural sources although these are quantitatively uncertain. As haloacetates are highly soluble in water, hydrometeors are most significant for their deposition. Fogwater (96 samples) and rainwater samples (over 100 samples) were collected from July 1998 to March 1999 at an ecological research site in northeastern Bavaria, Germany. They were analyzed for monofluoroacetate (MFA), difluoroacetate (DFA), trifluoroacetate (TFA), monochloroacetate (MCA), dichloroacetate (DCA), trichloroacetate (TCA), monobromoacetate (MBA), and dibromoacetate (DBA). The major inorganic ions were also determined. High concentrations of up to 11 microg/L MCA, 5 microg/L DCA, 2 microg/L TCA, and 2 microg/L TFA were found in fogwater associated with westerly winds. Backward trajectories were calculated to determine the origin of the air masses. MBA and DBA have highest concentrations in fogwater advected with air originating from the Atlantic, suggesting the marine origin of these two compounds. All analyzed substances show higher average concentrations in fog than in rain. Estimates of the deposition of haloacetates suggest that the contribution of fog may be more important than rain for the total burden of a forest ecosystem.     

The impact of aerosol composition on the particle to gas partitioning of reactive mercury

A laboratory system was developed to study the gas-particle partitioning of reactive mercury (RM) as a function of aerosol composition in synthetic atmospheric particulate matter. The collection of RM was achieved by filter- and sorbent-based methods. Analyses of the RM collected on the filters and sorbents were performed using thermal extraction combined with cold vapor atomic fluorescence spectroscopy (CVAFS), allowing direct measurement of the RM load on the substrates. Laboratory measurements of the gas-particle partitioning coefficients of RM to atmospheric aerosol particles revealed a strong dependence on aerosol composition, with partitioning coefficients that varied by orders of magnitude depending on the composition of the particles. Particles of sodium nitrate and the chlorides of potassium and sodium had high partitioning coefficients, shifting the RM partitioning toward the particle phase, while ammonium sulfate, levoglucosan, and adipic acid caused the RM to partition toward the gas phase and, therefore, had partitioning coefficients that were lower by orders of magnitude.     

Disinfection byproduct relationships and speciation in chlorinated nanofiltered waters

The formation and speciation of disinfection byproducts (DBPs) resulting from chlorination of nanofilter permeates obtained from various source water locations and membrane types are examined. Specific ultraviolet absorbance and bromide utilization are shown to decrease following nanofiltration. Both dissolved organic carbon (DOC) concentration and ultraviolet absorbance at 254 nm were found to correlate strongly with trihalomethane (THM), haloacetic acid (HAA), and total organic halide (TOX) concentrations in chlorinated nanofilter permeates, suggesting that they can be employed as surrogates for DBPs in nanofiltered waters. Because smooth curves were obtained for individual THM and HAA species as well as bromine and chlorine incorporation into THMs and HAAs as a function of Br-/DOC molar ratio, it is likely that mole fractions of these DBPs are more strongly influenced by chlorination conditions, Br-, and DOC concentrations than NOM source and membrane type. Mole fractions of mono-, di-, and trihalogenated HAAs were found to be independent of Br-/DOC. Even at a very low Br-/DOC of 2.9microM/mM, the mixed bromochloro- and tribromoacetic acids constituted 20% of total HAAs on a molar basis. This increased to approximately 50% as Br-/DOC increased to approximately 25microM/mM or more, proving that a large fraction of HAAs may not be covered under existing federal regulations. Total THM and HAA9 concentrations decreased in permeate waters with increasing Br-/DOC suggesting that nanofilter permeates are limited with respect to DBP precursors.     

Modeling aerosol formation from alpha-pinene + NOx in the presence of natural sunlight using gas-phase kinetics and gas-particle partitioning theory

A kinetic mechanism was used to link and model the gas-phase reactions and aerosol accumulation resulting from alpha-pinene reactions in the presence of sunlight, ozone (O3), and oxides of nitrogen (NOx). Reaction products and aerosol formation from the kinetic model were compared to outdoor smog chamber experiments conducted under natural sunlight in the presence of NOx and in the dark in the presence of O3. The gas-particle partitioning of semivolatile organics generated in the gas phase was treated as an equilibrium process between particle absorption and desorption. Models vs experimental aerosol yields illustrate that reasonable predictions of secondary aerosol formation are possible from both dark ozone and light NOx/alpha-pinene systems over a variety of different outdoor conditions. On average, measured gas- and particle-phase products accounted for approximately 54-72% of the reacted alpha-pinene carbon. Model predictions suggest that organic nitrates account for another approximately 25% of the reacted carbon, and most of this is in the gas phase. Measured particle-phase products accounted for 60-100% of the particle filter mass, with pinic acid and pinonic acid being the primary aerosol-phase products. In the gas phase, pinonaldehyde and pinonic acid are major products. Model simulations of these and other products show generally reasonable fits to the experimental data from the perspective of timing and concentrations. These results are very encouraging for a compound such as pinonaldehyde, since it is being formed from OH attack on alpha-pinene and is also simultaneously photolyzed and reacted with OH.     

Atmospheric gas-particle partitioning of polycyclic aromatic hydrocarbons in high mountain regions of Europe

Atmospheric concentrations and gas-particle partitioning of polycyclic aromatic hydrocarbons (PAH) have been determined at three remote mountain areas in Europe. Gas-phase mean concentrations of total PAH (20 individual compounds) were very similar at all sites, ranging from 1.3-2.6 ng m(-3) in the Pyrenees (Spain) to 2.7-3.7 ng m(-3) in the Alps (Austria) and Caledonian mountains (Norway). A seasonal variability was observed, with the highest levels found in winter. The seasonal differences were reflected better in the particle-associated PAH, showing the increase of PAH emissions in the colder months and a temperature dependence of the gas-particle partitioning. Significant geographical differences were also observed for particulate PAH, indicating a greater influence of regional sources than in the gas phase. Partitioning of PAH between gas and particulate phases was well-correlated with the subcooled liquid vapor pressure in all samples, but with slopes significantly steeper than the expected value of -1. These steeper slopes may reflect the occurrence of a nonexchangeable PAH fraction in the aerosols, likely associated to the soot carbon phase. Comparison of absorption to organic matter and soot carbon using the octanol-air (Koa) and soot-air (Ksa) partitioning coefficients shows that, despite uncertainties on estimated organic matter and soot carbon contents in the sampled aerosols, Koa underpredicts aerosol PAH concentrations by a factor of 0.6-2 log units. In contrast, predicted and measured high mountain aerosol PAH differ by 0.2-0.6 log units when Ksa is considered. The results point to soot carbon as the main transport medium for the long-range distribution of aerosol-associated PAH.     

Atmospheric concentrations and deposition of trichloroacetic acid in Scotland: results from a 2-year sampling campaign

The first long-term concurrent measurements of trichloroacetic acid (TCA) in rainwater, in cloudwater, and in air (both gas and particle phase) are reported. Measurements were made weekly between June 1998 and April 2000 at a rural forested upland site in SE Scotland. Rainwater TCA concentration did not differ significantly between two elevations (602 and 275 m asl), with precipitation-weighted mean values of 0.77 and 0.70 microg L(-1), respectively (n > 75). The precipitation-weighted mean concentration of TCA in cloudwater at the highest elevation was 0.92 microg L(-1), yielding an average cloudwater enrichment factor of 1.2, considerably lower than for other inorganic ions measured. Rainwater and cloudwater TCA concentrations did not vary systematically with season. Since wet precipitation depth also did not vary systematically with season, the wet deposition fluxes of TCA were likewise invariant (annual fluxes at the highest elevation of 880 and 130 microg m(-2), respectively, for rain and cloud interception to spruce forest). Weekly integrated concentrations of TCA in air (gas and particle) were very low (median 25 pg m(-3), range < LOD-110 pg m(-3)). The estimated upper limit for annual dry deposition of TCA at this site was approximately 20 microg m(-2), assuming a deposition velocity of 2 cm s(-1). Concentrations of TCA in air correlated reasonably strongly with concentrations in rainwater, with a partition ratio approximately equal to the Henry's law coefficient. On average, only about 23% of TCA measured in Edinburgh air was associated with the particle phase. These measurements are consistent with the observed high scavenging ratio of TCA (ratio of concentration in air to concentration in rainwater). Overall, these data confirm that the atmosphere is an important source of TCA to the environment and that precipitation is the dominant transfer mechanism. In line with previous work, the atmospheric deposition flux is greater than expected from the current understanding of atmospheric production of TCA from anthropogenic precursors. It is suggested that aqueous-phase processes could lead to greater atmospheric conversion of chlorinated solvent precursors to TCA than is currently accepted.     

Formation and mitigation of heterocyclic aromatic amines in fried pork

Heterocyclic aromatic amines (HAAs) are potent mutagens and carcinogens generated during the heat processing of meat. HAAs, which are abundant in processed meat products, include 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx), and 2-amino-1-methyl-6-phenylimidazo [4,5-b] pyridine (PhIP). The content of these three HAAs in fried pork was determined by LC-MS/MS. The effects of frying time and temperature, sample shape, and addition of antioxidants on the generation of HAAs were investigated. The results show that HAAs were produced during frying, and their levels increased with increasing frying time and temperature. Pork patties had the highest concentration of HAAs compared with pork meatballs and pork strips. The addition of antioxidant of bamboo leaves (AOB), liquorice extract, tea polyphenol, phytic acid and sodium iso-ascorbate to pork before frying had an inhibitory effect on HAA generation, with AOB being the most effective antioxidant. Inhibition levels of nearly 69.73% for MeIQx, 53.59% for 4,8-DiMeIQx and 77.07% for PhIP in fried pork were achieved when the concentrations of AOB added were 0.02, 0.01 and 0.10 g kg^?1, respectively.     

Atmospheric organochlorine pesticide concentrations near the Great Lakes: temporal and spatial trends

As a part of the Integrated Atmospheric Deposition Network, atmospheric organochlorine pesticide concentrations were measured in both the gas and particle phases at seven sites near the Great Lakes. Much higher organochlorine pesticide concentrations were found in the gas phase compared to that in the particle phase. Long-term decreasing trends were observed for most pesticides in both phases. Two different seasonal trends were observed in the particle phase: (a) in-use pesticides, such as endosulfan, showed higher concentrations in the summer, a time corresponding to their agriculture use, and (b) restricted organochlorine pesticides, such as lindane, showed higher particle-phase concentrations in the winter, presumably due to their enhanced partitioning from the gas phase to particles. Generally, Chicago had the highest concentrations of chlordanes, dieldrin, and sigmaDDT, suggesting that urban areas could be sources of these compounds to atmosphere. Point Petre had the highest concentrations of endosulfan, likely due to its agricultural application in Southern Ontario.     

Heterocyclic aromatic amine contents and quality characteristics of bacon as influenced by NaCl concentration of brine

Bacon usually have a high salt content. Excessive intake of salt could cause a harm to human health. Heterocyclic aromatic amines (HAAs) are carcinogenic and mutagenic heterocyclic compounds formed by the reactions of precursor substances at high temperature. This study investigated the influence of different levels of NaCl on the HAA contents and quality characteristics of bacon. Moisture, a_w, L* value, b* value, thiobarbituric acid-reactive substance (TBARS), and carbonyl content increased significantly with a decrease in the NaCl concentration of the brine (p < 0.05). There were no significant differences between treatments for a* value, pH, creatine content, sensory redness, bitterness, or off-odor (p > 0.05). Sensory evaluation showed that saltiness in bacon increased significantly with increased NaCl concentrations in brine. The increased NaCl concentrations decreased the total HAAs in fried bacon (p < 0.05). Moreover, the nonpolar HAA contents in bacon were higher than the polar HAA contents; salt concentration mainly affected the nonpolar HAA content. In summary, salt content had a significant influence on the HAA content and the quality characteristic of bacon.     

Inhalation exposure to haloacetic acids and haloketones during showering

Inhalation exposure to haloacetic acids (HAAs) and haloketones (HKs) in contaminated drinking water occurs during showering. The size distribution of the aerosols generated by a shower was determined using an eight size-range particle counter, which measured particles from 0.1 to >2 microm. An exponential increase in aerosol numbers was observed while the shower water was on, while the aerosol numbers declined exponentially once the water was turned off. The half-lives of the shower aerosols were longer than 5 min after the shower water was turned off. Although the majority of the shower-generated aerosols were smaller than 0.3 microm, these aerosols only contributed approximately 2% to the measured total aerosol mass. The total shower-generated particulate HAA and HK concentrations collected on an open face filter were approximately 6.3 and 0.13 microg/m3, respectively, for shower water HAA and HK concentrations of 250 and 25 microg/L, respectively. The vapor-phase HK concentrations were 25-50 microg/m3. The estimate of the dose from inhalation exposure of disinfection byproducts (DBPs) in the particulate phase indicate that they represent less than 1% of the ingestion dose, so inhalation is not expected to be an important exposure route to nonvolatile water contaminants or the portion of volatile DBPs that stay in the particulate phase, unless the lung is the target organ. The vapor-phase levels of volatile HKs, though, are significantly higher and can contribute greater than 10% of the ingestion dose during a shower. Thus, risk assessment to the these DBPs needs to consider the inhalation route.     

Reactions of semivolatile organics and their effects on secondary organic aerosol formation

Secondary organic aerosol (SOA) constitutes a significant fraction of total atmospheric particulate loading, but there is evidence that SOA yields based on laboratory studies may underestimate atmospheric SOA. Here we present chamber data on SOA growth from the photooxidation of aromatic hydrocarbons, finding that SOA yields are systematically lower when inorganic seed particles are not initially present. This indicates that concentrations of semivolatile oxidation products are influenced by processes beyond gas-particle partitioning, such as chemical reactions and/or loss to chamber walls. Predictions of a kinetic model in which semivolatile compounds may undergo reactions in both the gas and particle phases in addition to partitioning are qualitatively consistent with the observed seed effect, as well as with a number of other recently observed features of SOA formation chemistry. The behavior arises from a kinetic competition between uptake to the particle phase and reactive loss of the semivolatile product. It is shown that when hydrocarbons react in the absence of preexisting organic aerosol, such loss processes may lead to measured SOA yields lower than would occur under atmospheric conditions. These results underscore the need to conduct studies of SOA formation in the presence of atmospherically relevant aerosol loadings.     

Long-range atmospheric transport of polycyclic aromatic hydrocarbons: a global 3-d model analysis including evaluation of arctic sources

We use the global 3-D chemical transport model GEOS-Chem to simulate long-range atmospheric transport of polycyclic aromatic hydrocarbons (PAHs). To evaluate the model's ability to simulate PAHs with different volatilities, we conduct analyses for phenanthrene (PHE), pyrene (PYR), and benzo[a]pyrene (BaP). GEOS-Chem captures observed seasonal trends with no statistically significant difference between simulated and measured mean annual concentrations. GEOS-Chem also captures variability in observed concentrations at nonurban sites (r = 0.64, 0.72, and 0.74, for PHE, PYR, and BaP). Sensitivity simulations suggest snow/ice scavenging is important for gas-phase PAHs, and on-particle oxidation and temperature-dependency of gas-particle partitioning have greater effects on transport than irreversible partitioning or increased particle concentrations. GEOS-Chem estimates mean atmospheric lifetimes of <1 day for all three PAHs. Though corresponding half-lives are lower than the 2-day screening criterion for international policy action, we simulate concentrations at the high-Arctic station of Spitsbergen within four times observed concentrations with strong correlation (r = 0.70, 0.68, and 0.70 for PHE, PYR, and BaP). European and Russian emissions combined account for ～80% of episodic high-concentration events at Spitsbergen.     

Heterocyclic Aromatic Amines in Cooked Meat Products: Causes,Formation, Occurrence,and Risk Assessment

Meat products are sources of protein with high biological value and an essential source of other nutrients, such as vitamins and minerals. Heating processes cause food to become more appetizing with changes in texture, appearance, flavor, and chemical properties by the altering of protein structure and other ingredients. During heat treatment, heterocyclic aromatic amines (HAAs), potent mutagens/carcinogens, are formed due to the Maillard reaction. The HAAs are classified in at least 2 groups: thermic HAAs (100 to 300 °C) and pyrolytic HAAs (>300 °C). This review focuses on the parameters and precursors which affect the formation of HAAs: preparation, such as the marinating of meat, and cooking methods, including temperature, duration, and heat transfer, as well as levels of precursors. Additionally, factors are described subject to pH, and the type of meat and ingredients, such as added antioxidants, types of carbohydrates and amino acids, ions, fat, and other substances inhibiting or enhancing the formation of HAAs. An overview of the different analytical methods available is shown to determine the HAAs, including their preparation to clean up the sample prior to extraction. Epidemiological results and human daily intake of HAAs obtained from questionnaires show a relationship between the preference for very well‐done meat products with increased HAA levels and an enhanced risk of the incidence of cancer, besides other carcinogens in the diet. The metabolic pathway of HAAs is governed by the activity of several enzymes leading to the formation of DNA adducts or HAA excretion and genetic sensitivity of individuals to the impact of HAAs on human cancer risk.     

Regressing gas/particle partitioning data for polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAHs) were measured in the rural atmosphere of Southern Ontario, Canada from October 2001 to November 2002. Sixty seven pairs of gaseous and particle-bound concentrations of PAHs were determined concurrently in a forest and a clearing. The gas/particle partitioning behavior of the PAHs was investigated by fitting the original Junge-Pankow equation to the fraction in the particle phase phi for each set of measured data, either allowing the slope m to deviate from -1 (two-parameter model) or not (one-parameter model). This fitting procedure was judged more robust than linear logarithmic regressions involving the gas/particle partition coefficient, because the latter is sensitive to the applied blank correction, tends to ignore a significant amount of analytical information, and gives undue weight to more uncertain data points. The experimental data fit was good for both nonlinear models, and discrepancies between experimental data and models and between models are mostly related to sampling/experimental artifacts. In particular, samples taken close to the freezing point appear to suffer from blow-off artifacts. Applying slopes m different from -1 appears only justified if it can be assured that a second parameter indeed provides a better fit and that this better fit is not due to experimental, analytical, or statistical artifacts. The magnitude of the differences in the model fitting parameters between sampling events is consistent with the reported variability in the nature and concentration of atmospheric particles. Statistical tests on the regression results indicate that the gas/particle partitioning was not significantly different between the forest and the clearing.     

Influence of selected quality factors of beef on the profile and the quantity of heterocyclic aromatic amines during processing at high temperature

New factors were identified impacting significantly on the formation of HAA during grilling. The number and profile of HAA in grilled beef depend on the fattening system (intensive and semi-intensive), and the effect of the animal’s sex. The fewest HAAs were formed in rib steak from heifers from a semi-intensive fattening system. A significant effect of storage of meat in refrigerated conditions (5 to 15 days) was also demonstrated on the formation of HAA during grilling. The longer the raw meat was stored, the more HAA was formed during grilling. The quantity of HAA was strongly correlated with the content of free amino acids and a very strong correlation was found with an increasing content of free purine and pyrimidine bases and their nucleosides.     

Response surface optimization of effects of some processing variables on carcinogenic/mutagenic heterocyclic aromatic amine (HAA) content in cooked patties

A five-factor Central Composite Orthogonal Design was adopted to study simultaneous effects of some processing variables such as NaCl (0-2%), fat (10-30%), ascorbic acid (0-600 ppm), cooking temperature (150-230°C) and cooking time (5-15 min) on physicochemical properties and heterocyclic aromatic amine (HAA) contents of cooked beef patties. The HAAs analyzed were 2-amino-3-methylimidazo[4,5-f]-quinoline (IQ), 2-amino-3,8-dimethylimidazo[4,5-f]-quinoxaline (MeIQx), 2-amino-3,4-dimethylimidazo[4,5-f]-quinoline (MeIQ), 2-amino-3,4,8-trimethylimidazo[4,5-f]-quinoxaline (4,8-DiMeIQx) and 2-amino-1-methyl-6-phenylimidazo[4,5-b]-pyridine (PhIP), as quantified by high-performance liquid chromatography with photo-diode array detection (HPLC-UV/DAD). It was found that ascorbic acid decreased; however, fat, cooking temperature and time levels increased the contents of IQ, MeIQx, MeIQ and PhIP. In addition, estimated ridge analysis was conducted to find values of the processing variables that maximize and minimize the five HAA contents, revealing that the results obtained would be useful for meat industry aiming to decrease HAA content in cooked meat products.