Chloride and organic chlorine in forest soils: storage, residence times, and influence of ecological conditions

Recent studies have shown that extensive chlorination of natural organic matter significantly affects chlorine (Cl) residence time in soils. This natural biogeochemical process must be considered when developing the conceptual models used as the basis for safety assessments regarding the potential health impacts of 36-chlorine released from present and planned radioactive waste disposal facilities. In this study, we surveyed 51 French forested areas to determine the variability in chlorine speciation and storage in soils. Concentrations of total chlorine (Cl(tot)) and organic chlorine (Cl(org)) were determined in litterfall, forest floor and mineral soil samples. Cl(org) constituted 11-100% of Cl(tot), with the highest concentrations being found in the humus layer (34-689 mg Cl(org) kg(-1)). In terms of areal storage (53 - 400 kg Cl(org) ha(-1)) the mineral soil dominated due to its greater thickness (40 cm). Cl(org) concentrations and estimated retention of organochlorine in the humus layer were correlated with Cl input, total Cl concentration, organic carbon content, soil pH and the dominant tree species. Cl(org) concentration in mineral soil was not significantly influenced by the studied environmental factors, however increasing Cl:C ratios with depth could indicate selective preservation of chlorinated organic molecules. Litterfall contributions of Cl were significant but generally minor compared to other fluxes and stocks. Assuming steady-state conditions, known annual wet deposition and measured inventories in soil, the theoretical average residence time calculated for total chlorine (inorganic (Cl(in)) and organic) was 5-fold higher than that estimated for Cl(in) alone. Consideration of the Cl(org) pool is therefore clearly important in studies of overall Cl cycling in terrestrial ecosystems.     

Chloride retention and release in a boreal forest soil: effects of soil water residence time and nitrogen and chloride loads

The common assumption that chloride (Cl-) is conservative in soils and can be used as a groundwater tracer is currently being questioned, and an increasing number of studies indicate that Cl- can be retained in soils. We performed lysimeter experiments with soil from a coniferous forest in southeast Sweden to determine whether pore water residence time and nitrogen and Cl- loads affected Cl- retention. Over the first 42 days there was a net retention of Cl- with retention rates averaging 3.1 mg CI- m(-2) d(-1) (68% of the added Cl- retained over 42 days). Thereafter, a net release of Cl- at similar rates was observed for the remaining experimental period (85 d). Longer soil water residence time and higher Cl- load gave higher initial retention and subsequent release rates than shorter residence time and lower Cl- load did. Nitrogen load did not affect Cl transformation rates. This study indicates that simultaneous retention and release of Cl- can occur in soils, and that rates may be considerable relative to the load. The retention of Cl- observed was probably due to chlorination of soil organic matter or ion exchange. The cause of the shift between net retention and net release is unclear, but we hypothesize that the presence of O2 or the presence of microbially available organic matter regulates Cl- retention and release rates.     

Assessing the reactivity of free chlorine constituents Cl₂, Cl₂O, and HOCl toward aromatic ethers

Cl(2) and Cl(2)O are highly reactive electrophiles capable of influencing rates of disinfection byproduct (DBP) precursor chlorination in solutions of free available chlorine (FAC). The current work examines how organic compound structure influences susceptibility toward chlorination by Cl(2) and Cl(2)O relative to the more abundant (but less reactive) electrophile HOCl. Chlorination rates and products were determined for three aromatic ethers, whose reactivities with FAC increased in the order: 3-methylanisole <1,3-dimethoxybenzene <1,3,5-trimethoxybenzene. Varying solution conditions (pH, [FAC], [Cl(-)]) permitted quantification of regiospecific second-order rate constants for formation of each product by Cl(2), Cl(2)O, and HOCl. Our results indicate that as the reactivity of methoxybenzenes decreases, the importance of Cl(2) and Cl(2)O (relative to HOCl) increases. Accordingly, Cl(2) and Cl(2)O are likely to play important roles in generating DBPs that originate from natural organic matter (NOM) constituents of somewhat moderate reactivity. As [Cl(2)] is proportional to [Cl(-)] and [Cl(2)O] is proportional to [HOCl](2), ramifications for DBP control measures may differ significantly for these precursors compared to more reactive NOM moieties likely to react predominantly with HOCl. In particular, the role of chloride as a chlorination catalyst challenges its traditional classification as an "inert" electrolyte in water treatment processes.     

Chlorine isotope fractionation during reductive dechlorination of chlorinated ethenes by anaerobic bacteria

Chlorine isotope fractionation during reductive dechlorination of trichloroethene (TCE) and tetrachloroethene (PCE) to cis-1,2-dichloroethene (cDCE) by anaerobic bacteria was investigated. The changes in the 37Cl/35Cl ratio observed during the one-step reaction (TCE to cDCE) can be explained by the regioselective elimination of chlorine accompanied by the Rayleigh fractionation. The fractionation factors (alpha) of the TCE dechlorination by three kinds of anaerobic cultures were approximately 0.994-0.995 at 30 degrees C. The enrichment of 37Cl in the organic chlorine during the two-step reaction (PCE to cDCE) can be explained by the random elimination of one chlorine atom in the PCE molecule followed by the regioselective elimination of one chlorine atom in the TCE molecule. The fractionation factors for the first step of the PCE dechlorination with three kinds of anaerobic cultures were estimated to be 0.987-0.991 at 30 degrees C using a mathematical model. Isotope fractionation during the first step would be the primary factor for the chlorine isotope fractionation during the PCE dechorination to cDCE. The developed models can be utilized to evaluate the fractionation factors of regioselective and multistep reactions.     

Long-term recovery of PCB-contaminated sediments at the Lake Hartwell superfund site: PCB dechlorination. 2. Rates and extent

This paper reports on extensive polychlorinated biphenyl (PCB) dechlorination measured in Lake Hartwell (Pickens County, SC) sediments. Vertical sediment cores were collected from 18 locations in Lake Hartwell (Pickens County, SC) and analyzed in 5-cm increments for PCB congeners. The preferential loss of meta and para chlorines with sediment depth demonstrated that PCBs in the sediments underwent reductive dechlorination after burial. Notably, ortho chlorines were highly conserved for more than 5 decades; since the first appearance of PCBs, ca. 1950-1955. These dechlorination characteristics resulted in the accumulation of lower chlorinated congeners dominated by ortho chlorine substituents. Dechlorination rates were determined by plotting the numbers of meta plus para chlorines per biphenyl molecule (mol of chlorine/mol of PCB) with sediment age. Regression analyses showed linear correlations between meta plus para chlorine concentrations with time. The average dechlorination rate was 0.094 +/- 0.063 mol of Cl/mol of PCB/yr. The rates measured using the 2001 cores were approximately twice those measured using the 2000 cores, most likely because the 2001 cores were collected only at transects O, L, and I, which had the highest rates measured in 2000. An inverse of the dechlorination rates indicated that 16.4 +/- 11.6 yr was required per meta plus para chlorine removal (ranging from 4.3 to 43.5 yr per chlorine removal). The rates determined from this study were 1-2 orders of magnitude lower than rates reported from laboratory microcosm studies using Hudson River and St. Lawrence River sediments, suggesting that dechlorination rates reported for laboratory experiments are much higher than those occurring in situ.     

Bonding of ppb levels of methyl mercury to reduced sulfur groups in soil organic matter

The strong binding of CH3Hg+ to natural organic matter (NOM) in soils and waters determines the speciation of CH3Hg under aerobic conditions and indirectly its bioavailability and rates of demethylation. In lab experiments, halides (Cl, Br, I) were used as competing ligands to determine the strength of CH3Hg+ binding to solid-phase soil organic carbon (SOC) and to dissolved soil organic carbon (DOC) as a function of time, pH, and concentration of halide. Experiments were conducted with native concentrations of CH3Hg (1.7-9.8 ng g(-1)) in organic soils, and equilibrium concentrations of CH3Hg were determined by species-specific-isotope-dilution (SSID) gas-chromatography-induced-coupled-plasma-mass-spectrometry (GC-ICP-MS). A simple model (RS- + CH3Hg+ = CH3HgSR; log KCH3HgSR) was used to simulate the binding to SOC and DOC, in which the binding sites (RSH) were independently determined by X-ray absorption near-edge structure (XANES) spectroscopy. The pKa values of RSH groups were fixed at 8.50 and 9.95, reflecting the two major thiol groups in proteins. Log KCH3HgSR values determined for SOC and DOC were similar, showing a range of 15.6-17.1 for all experiments covering a pH range of 2.0-5.1. Despite large differences in affinities between Cl, Br, and I for CH3Hg+, determined constants were independent of type and concentration of halide used in the experiments (log KCH3HgSR = 16.1-16.7 at pH 3.5-3.6). Even if our log KCH3HgSR values were conditional in that they decreased with pH above 3.5, they were in fair agreement with stability constants determined for the association between CH3Hg+ and thiol groups in well-defined organic molecules (log K1 = 15.7-17.5). Speciation calculations based on our results show that, in absence of substantial concentrations of inorganic sulfides, neutral chloro-complexes (CH3HgCl) and free CH3Hg+ reach concentrations on the order of 10(-17)-10(-18) M at pH 5 in soil solutions with 3 x 10(-5) M of chloride.     

Fate of prions in soil: interactions of RecPrP with organic matter of soil aggregates as revealed by LTA-PAS

The contribution of soil organic matter (OM) to the adsorption of a recombinant prion protein (RecPrP) was studied in microcosm systems (soil aggregates from two different soils) before and after OM removal by low temperature ashing (LTA). The LTA technique allows a controlled removal of OM layer by layer, like a peeling of an onion skin, with minimal disturbance of the mineral matrix. Soil aggregates were selected as a representative model of the "in situ" conditions. Adsorption from batch vs percolation experiments were compared, and the aggregates were characterized by photoacustic Fourier-transform IR spectroscopy (PAS-FTIR). High affinity (H-type) adsorption isotherms were found with complete removal of RecPrP from solution for protein/soil ratios up to 1:62.5. OM removal from aggregates decreased the adsorbed RecPrP in amounts corresponding to 330-1000 microg mg(-1) of soil organic carbon (OC) indicating that native OM has specific adsorption capacity comparable and/or superior to the mineral matrix. The coupled LTA-PAS-FTIR approach demonstrated that, albeit OM composition was homogeneous throughout the aggregates, its presence in the most external surfaces of the aggregates affects the diffusion dynamics of RecPrP within the aggregates during percolation.     

Relationships between soil organic matter, nutrients, bacterial community structure, and the performance of microbial fuel cells

Microbial fuel cells (MFCs) offer the potential for generating electricity, mitigating greenhouse gas emissions, and bioremediating pollutants through utilization of a plentiful renewable resource: soil organic carbon. We analyzed bacterial community structure, MFC performance, and soil characteristics in different microhabitats within MFCs constructed from agricultural or forest soils in order to determine how soil type and bacterial dynamics influence MFC performance. Our results indicated that MFCs constructed from agricultural soil had power output about 17 times that of forest soil-based MFCs and respiration rates about 10 times higher than forest soil MFCs. Agricultural soil MFCs had lower C:N ratios, polyphenol content, and acetate concentrations than forest soil MFCs. Bacterial community profile data indicate that the bacterial communities at the anode of the high power MFCs were less diverse than in low power MFCs and were dominated by Deltaproteobacteria, Geobacter, and to a lesser extent, Clostridia, while low-power MFC anode communities were dominated by Clostridia. These results suggest that the presence of organic carbon substrate (acetate) was not the major limiting factor in selecting for highly electrogenic bacterial communities, while the quality of available organic matter may have played a significant role in supporting high performing bacterial communities.     

Role of soil health in maintaining environmental sustainability of surface coal mining

Mountaintop coal mining (MCM) in the Southern Appalachian forest region greatly impacts both soil and aquatic ecosystems. Policy and practice currently in place emphasize water quality and soil stability but do not consider upland soil health. Here we report soil organic carbon (SOC) measurements and other soil quality indicators for reclaimed soils in the Southern Appalachian forest region to quantify the health of the soil ecosystem. The SOC sequestration rate of the MCM soils was 1.3 MgC ha(-1) yr(-1) and stocks ranged from 1.3 ± 0.9 to 20.9 ± 5.9 Mg ha(-1) and contained only 11% of the SOC of surrounding forest soils. Comparable reclaimed mining soils reported in the literature that are supportive of soil ecosystem health had SOC stocks 2.5-5 times greater than the MCM soils and sequestration rates were also 1.6-3 times greater. The high compaction associated with reclamation in this region greatly reduces both the vegetative rooting depth and infiltration of the soil and increases surface runoff, thus bypassing the ability of soil to naturally filter groundwater. In the context of environmental sustainability of MCM, it is proposed that the entire watershed ecosystem be assessed and that a revision of current policy be conducted to reflect the health of both water and soil.     

Formation and extraction of persistent fumigant residues in soils

Fumigants are commonly thought to be short-lived in soil, but residues have been found in soils years following application. In this study, formation and extraction of persistent soil fumigant residues were investigated. Fumigants 1,3-dichloropropene (1,3-D), chloropicrin (CP), and methyl isothiocyanate (MITC) were spiked into Arlington, Glenelg, and Hagerstown soils and incubated for 30 d under controlled conditions. The incubated soils were evaporated for 20 h prior to extraction with a variety of organic solvents at different temperatures. Extraction with acetonitrile in sealed vials at 80 degrees C for 24 h was the most efficient method to recover persistent soil fumigant residues. At application rates of 1000-1700 mg (kg of soil)(-1), persistent residues of 1,3-D, CP, and MITC in the three soils ranged from 5 to 67 mg kg(-1). The residue content increased with application rate, correlated positively with soil silt content, decreased dramatically as indigenous organic matter (OM) was removed, and changed little with external OM addition. Adsorption to clay surfaces was not important in fumigant retention, while pulverization of soil aggregates significantly decreased persistent fumigant residues. The results suggest that persistent fumigant residues are retained in soil intra-aggregate micropores resulting from binding clay flocs and silt particles by humic substances.     

Production of macromolecular chloramines by chlorine-transfer reactions

Chlorination of treated wastewaters is undertaken to prevent dispersal of human pathogens into the environment. Except in well-nitrified effluents, the primary agents in chlorination, Cl2(g) or NaOCl(aq), are short-lived and quickly transfer oxidative chlorine to secondary agents (N-chloramines), which then participate in the disinfection process. Maturation of residual chlorine resulting from chlorine-transfer reactions is still poorly characterized. Using gel permeation and reversed-phase liquid chromatography combined with a novel, oxidant-specific detector, unanticipated trends during the maturation of residual chlorine in wastewater are identified. Within 2 min after addition of NaOCl, and continuing for several hours at least, significant amounts of oxidative chlorine are transferred to secondary agents that are moderately to strongly hydrophobic and to agents that have high relative molecular masses (Mr 1300-25000). It is hypothesized that hydrophobic stabilization of organic chloramines (RNHCl(o)) thermodynamically drives these transfers, making macromolecular chloramines the ultimate oxidative chlorine carriers. Macromolecular chloramines are expected to be sluggish oxidants, as observed in their reduction by sulfite, and are expected to be poor disinfectants. If transfer of oxidative chlorine to high Mr components occurs widely at treatment plants, then this phenomenon offers a new, physicochemical explanation for the well-known impotency of organic chloramines in wastewater disinfection.     

I-THM formation and speciation: preformed monochloramine versus prechlorination followed by ammonia addition

An increasing number of utilities in the United States have been switching from chlorination to chloramination practices to comply with the more stringent trihalomethane (THM) and haloacetic acid (HAA) regulations. This has important implications for disinfection byproduct (DBP) formation because the reactions of chlorine and monochloramine (NH(2)Cl) with natural organic matter (NOM) are not the same. In this study, iodinated trihalomethane (I-THM) formation from preformed NH(2)Cl and prechlorination (at two chlorine doses and contact times) followed by ammonia addition was compared. A representative bromide/iodide ratio of 10:1 was selected and four bromide/iodide levels (ambient, 50/5 or 100/10, 200/20, and 800/80 [μg/L/μg/L]) were evaluated. The results showed that I-THM formation was generally lower for prechlorination as compared to preformed NH(2)Cl due to the oxidation of iodide to iodate by chlorine. However, while prechlorination minimized iodoform (CHI(3)) formation, prechlorination sometimes formed more I-THMs as compared to preformed NH(2)Cl due to a large increase in the formation of brominated I-THM species, which were formed at much smaller amounts from preformed NH(2)Cl. I-THM concentrations and speciation for the two chloramination scenarios (i.e., preformed NH(2)Cl vs prechlorination followed by ammonia) depended on chlorine dose, contact time, bromide/iodide concentration, and NOM characteristics of the source water (SUVA(254)).     

Chlorinated paraffins in sediments from the Pearl River Delta, South China: spatial and temporal distributions and implication for processes

Short-chain and medium-chain chlorinated paraffins (SCCPs and MCCPs) were measured in sediments from ponds, rivers and tributaries, and an estuary, as well as a sediment core in the Pearl River Delta (PRD), South China, to comprehensively investigate the spatial and temporal distributions of CPs. The concentrations of SCCPs and MCCPs in sediment were varied from 320 to 6600 ng/g and from 880 to 38,000 ng/g, respectively. Elevated CP concentrations were found in pond sediments (means of 2800 and 21,000 ng/g for SCCPs and MCCPs) in the e-waste recycling area and in river sediments (means of 1200 and 3900 ng/g for SCCPs and MCCPs) in the highly industrialized areas. The significant positive correlations between SCCP concentration and MCCPs/SCCPs in the highly industrialized areas reflected the emission of local industry activities, while the significant negative correlations in the low industrial activity areas could be linked to long-range transportation of CPs. An increased abundance of short chain and low chlorinated congeners was observed in the low industrial activity areas compared to the industrialized areas. The preferred transportation of short chain and low chlorinated congener CPs and the dechlorination of higher chlorinated congeners CPs were the most likely reasons. The vertical profile of CPs in the sediment core indicated a rapid increase in the usage of CPs and a shift to more MCCPs in recent years. The decreased chlorine content of CPs with increasing sediment depth indicated the possibility of dechlorination of higher chlorinated congeners (Cl(9) and Cl(10)) after deposition in sediments with greater dechlorination potential for short chain CPs than long chain CPs.     

Effect of two organic amendments on norflurazon retention and release by soils of different characteristics

The influence of two organic amendments on norflurazon sorption-desorption processes in four soils with very different physicochemical characteristics was studied in laboratory experiments to evaluate the potential leaching of this pesticide through organic fertilized soils. Sorption-desorption experiments were performed on original soils and on a mixture of these soils with urban waste compost (SUW) and a commercial amendment from olive-mill wastes (OW), at a rate of 6.25% (w/w). These mixtures were used immediately after preparation and after aging for 2 months. Norflurazon was analyzed by using a HPLC method. Norflurazon retention in original soils was related not only to the organic matter (OM) content but also to mineral surfaces present in soils. Norflurazon sorption increases largely after amendment in soils with low OM content, but the addition of exogenous OM to soils with medium OM content and/or other available adsorptive surfaces did not significantly affect norflurazon sorption. Even in some cases pesticide sorption decreases, due to the blocking of the mineral and organic soil surfaces with the amendment added. Transformation of exogenous OM during incubation depends both on the amendment added and on the type of soil and can affect sorption-desorption behavior of the soils surfaces in different manner, due to the modification of their hydrophobic-hydrophilic characteristics. Norflurazon desorption from original soils showed hysteresis in all cases, but it was not affected or even decreased in amended soils. It was a nonexpected behavior, especially in sandy soil, since it is generally assumed that a higher sorption always implies a lower mobility in soils. Norflurazon sorption must be taking place on very low affinity sites on exogenous OM through weak bindings, from which the pesticide can be easily desorbed. The application to soils of the organic amendments used in the present study could not be accepted to reduce norflurazon losses due to leaching processes.     

Mechanism and kinetics of cyanogen chloride formation from the chlorination of glycine

Glycine is an important precursor of cyanogen chloride (CNCl)--a disinfection byproduct (DBP) found in chlorinated drinking water. To model CNCl formation from glycine during chlorination, the mechanism and kinetics of the reaction between glycine and free chlorine were investigated. Kinetic experiments indicated that CNCI formation was limited by either the decay rates of N,N-dichloroglycine or a proposed intermediate, N-chloroiminocarboxylate, CIN=CHCO2-. Only the anionic form of N,N-dichloroglycine, NCl2CH2CO2-, however, decays to form CNCl, while the protonated neutral species forms N-chloromethylimine. At pH > 6, glycine-nitrogen is stoichiometrically converted to CNCI, while conversion decreases at lower pH due to the formation of N-chloromethylimine. Under conditions relevant to drinking water treatment, i.e., at pH 6 to 8 and with free chlorine in excess, a simplified rate expression for the concentration of glycine-nitrogen converted to CNCl, [CNCl]f, applies: dt/d[CNCl]f = k2*[Cl2-Gly](T,o)exp(-k2*t) where [Cl2-Gly]T,o is the initial concentration of total N,N-dichloroglycine, k2* is the first-order decay constant for CIN=CHCO2-, k2*(s(-1)) = 10(12)(+/-4) exp(-1.0(+/-0.3) x 10(4)/T), and T is the absolute temperature in K. Kinetic expressions for d[CNCl]/dt when free chlorine is in excess, however, must also account for the significant decay of CNCl by hypochlorite-catalyzed hydrolysis, which has been characterized in previous studies. Although CNCl formation is independent of the free chlorine concentration, higher chlorine concentrations promote its hydrolysis.     

Influence of natural organic matter on As transport and retention

Natural organic matter (NOM) can affect the behavior of arsenic within surface and subsurface environments. We used batch and column experiments to determine the effect of peat humic acids (PHA), groundwater fulvic acids (GFA), and a soil organic matter (SOM) extract on As sorption/transport in ferrihydrite-coated sand columns. A reactive transport model was used to quantitatively interpret the transport of As in flow-through column (breakthrough) experiments. We found that As(III) breakthrough was faster than As(V) by up to 18% (with OM) and 14% (without OM). The most rapid breakthrough occurred in systems containing SOM and GFA. Dialysis and ultrafiltration of samples from breakthrough experiments showed that in OM-containing systems, As was transported mostly as free (noncomplexed) dissolved As but also as ternary As-Fe-OM colloids and dissolved complexes. In OM-free systems, As was transported in colloidal form or as a free ion. During desorption, more As(III) desorbed (23-37%) than As(V) (10-16%), and SOM resulted in the highest and OM-free systems the lowest amount of desorption. Overall, our experiments reveal that (i) NOM can enhance transport/mobilization of As, (ii) different fractions of NOM are capable of As mobilization, and (iii) freshly extracted SOM (from a forest soil) had greater impact on As transport than purified GFA/PHA.     

Iodate and iodo-trihalomethane formation during chlorination of iodide-containing waters: role of bromide

The kinetics of iodate formation is a critical factor in mitigation of the formation of potentially toxic and off flavor causing iodoorganic compounds during chlorination. This study demonstrates that the formation of bromine through the oxidation of bromide by chlorine significantly enhances the oxidation of iodide to iodate in a bromide-catalyzed process. The pH-dependent kinetics revealed species specific rate constants of k(HOBr + IO(-)) = 1.9 × 10(6) M(-1) s(-1), k(BrO(-) + IO(-)) = 1.8 × 10(3) M(-1) s(-1), and k(HOBr + HOI) < 1 M(-1) s(-1). The kinetics and the yield of iodate formation in natural waters depend mainly on the naturally occurring bromide and the type and concentration of dissolved organic matter (DOM). The process of free chlorine exposure followed by ammonia addition revealed that the formation of iodo-trihalomethanes (I-THMs), especially iodoform, was greatly reduced by an increase of free chlorine exposure and an increase of the Br(-)/I(-) ratio. In water from the Great Southern River (with a bromide concentration of 200 μg/L), the relative I-incorporation in I-THMs decreased from 18 to 2% when the free chlorine contact time was increased from 2 to 20 min (chlorine dose of 1 mg Cl(2)/L). This observation is inversely correlated with the conversion of iodide to iodate, which increased from 10 to nearly 90%. Increasing bromide concentration also increased the conversion of iodide to iodate: from 45 to nearly 90% with a bromide concentration of 40 and 200 μg/L, respectively, and a prechlorination time of 20 min, while the I-incorporation in I-THMs decreased from 10 to 2%.     

Influence of sorption to dissolved humic substances on transformation reactions of hydrophobic organic compounds in water. I. Chlorination of PAHs

The effect of sorption to dissolved humic acids (HAs) on the chlorination of PAHs in aqueous solution was studied. The addition of HA accelerated the chlorination of fluoranthene and naphthalene in hypochlorite solutions at pH 5, the stronger effect being observed for fluoranthene that is sorbed to a higher extent than naphthalene. Sorption coefficients (K(DOC)) of the analytes were determined by solid-phase microextraction (SPME). The observed rate constant for fluoranthene chlorination is, for example, larger by a factor of 5 in the presence of 10 mg L(-1) of an aquatic HA as compared to HA-free solution (k' = 0.02 h(-1) at 60 mg L(-1) active chlorine, pH 5, without HA). While Cl2 is the dominant reactive species in pure aqueous solution for both PAHs, the reaction of fluoranthene seems to involve an additional pathway of chlorination by HOCl in the presence of HA. It was found that not only did HA not protect PAHs from the electrophilic attack of the chlorinating species, but the sorption of PAHs on the hydrophobic domains of the HA favored instead the extent of the chlorination reaction.     

Cl K-edge X-ray spectroscopic investigation of enzymatic formation of organochlorines in weathering plant material

The contribution of halocarbons from plant weathering to the total organohalogen budget of terrestrial systems is gaining recognition. To evaluate the formation of such halocarbons, speciation of chlorine in Sequoia sempervirens (redwood) needles was examined in the presence of an external chloroperoxidase (CPO) enzyme using Cl K-edge X-ray absorption spectroscopy. The Cl forms in fresh and naturally weathered needles and in model laboratory reactions were compared. To provide a straightforward analogue to the enzymatic chlorination in plants, chlorination reactions were conducted for phenol, a common moiety of plant macromolecules. Plant material chlorination was also examined in the presence of hypochlorite in an ancillary mechanistic investigation. The dominant form of Cl in fresh, unreacted plant material was found to be inorganic Cl-, which was partially converted to organochlorine in the presence of CPO. Chlorination is affected by the nature of reactant (CPO, H2O2) addition, reaction time, and temperature. The organochlorines produced in these laboratory investigations closely resemble those produced during the natural weathering of redwood needles. A striking consistency in chlorine speciation observed among the various sample types suggests that (i) CPO produced by terrestrial organisms could play a vital role in the generation of organochlorines associated with the degradation of plant material and (ii) initial targets of enzymatic chlorination might include lignin-like macromolecules rich in aromatic character and hydroxyl groups. These findings lend further credibility to a significant biogenic contribution to the global organohalogen burden by elucidating a probable route of enzymatic chlorination of natural organic matter in terrestrial systems.     

Sorption of pyrene by regular and nanoscaled metal oxide particles: influence of adsorbed organic matter

Sorption of pyrene by regular and nanoscaled aluminum, zinc, and titanium oxides was examined. All oxides had low sorption for pyrene because of sorbed water molecules. Due to the larger surface area (SA) of nanoparticles, they had higher sorption for pyrene than the regular ones. Organic matter (OM) coating greatly enhanced pyrene sorption by all oxides, noting the importance of sorbed OM in sorption of hydrophobic organic compounds (HOCs). Due to higher sorption site density in the sorbed OM phase on the regular oxide surfaces, SA-normalized distribution coefficients (K(dSA)) of pyrene by OM-regular oxide complexes (6.0-40.6) were greater than the OM-coated oxide nanoparticles (0.7-12.5). Furthermore, the OM-regular oxide complexes had higher organic carbon content-normalized K(dSA) values of pyrene (48-17 300) than the OM-nanoscaled oxide complexes (15-1530). This variation may be due to different physical forms and fractionation of the loaded OM on regular and nanoscaled oxide particles.