Formation of chlorinated disinfection by-products in viticulture

Background, aim and scope  The use of sodium hypochlorite (HYP) in viticulture results in effluents which are contaminated with halogenated substances. These disinfection by-products (DBPs) can be quantified as group parameter ‘adsorbable organic halogens’ (AOX) and have not been determined in effluents of viticulture yet. The substances that are detected as AOX are unknown. The AOX can be composed of harmless substances, but even toxic contaminants. Thus, it is impossible to assess ecological impacts. The aim of this study is to determine the quantification of AOX and DBPs after the use of HYP. This will be helpful to reduce environmental pollution by AOX. Materials and methods  The potential of HYP to generate AOX was determined in laboratory-scale experiments. Different model solutions were treated with HYP according to disinfection processes in viticulture and conditions of AOX formation in effluents were simulated. AOX were quantified using the flask-shaking method and identified DBPs were investigated by gas chromatography–mass spectrometry. Results  Treatment with HYP resulted in the formation of AOX. The percentage conversion of HYP to AOX was up to 11%. Most important identified DBPs in viticulture are chloroform, dichloroacetic acid and trichloroacetaldehyde. In addition, the formation of carbon tetrachloride (CT), 1,1,1-trichloropropanone, 2,4-dichlorobenzoic acid and 2-chloro-/2,4-dichlorophenylacetic acid was investigated. It was demonstrated that reaction temperature, concentration of HYP and type of organic matter have important influence on the formation of chlorinated DBPs. Discussion  The percentage conversion of HYP to AOX was similar to other published studies. Although a correlation of single compounds and AOX is difficult, chloroform was the predominant AOX. Generation of the volatile chloroform should be avoided due to possible adverse effects. The generation of dichloroacetic acid is of minor importance on account of biodegradation. Trichloroacetaldehyde and 1,1,1-trichloropropanone are weak mutagens and their formation should be avoided. Conclusions  The generation of AOX and chlorinated DBPs can be minimised by reducing the concentrations of the organic materials in the effluents. The removal of organic matter before disinfection results in a decreased formation of AOX. HYP is an effective disinfectant; therefore, it should be used at low temperatures and concentrations to reduce the amount of AOX. If possible, disinfection should be accomplished by the use of no chlorine-containing agents. By this means, negative influences of HYP on the quality of wine can also be avoided. Recommendations and perspectives  Our results indicate that HYP has a high potential to form AOX in effluents of viticulture. The predominant by-products are chloroform, dichloroacetic acid and trichloroacetaldehyde. In further research, wastewaters from a winery and the in- and outflows of two sewage treatment plants were sampled during vintage and analysed. These results will be discussed in a following paper.     

Formation of nitrogenous disinfection by-products from pre-chloramination

A sampling survey investigated the formation of nitrogenous disinfection by-products (N-DBPs) and carbonaceous DBPs (C-DBPs) from pre-chloramination, an increasingly common treatment strategy in China for regulated C-DBP control, followed by subsequent conventional water treatment processes, i.e., coagulation, sedimentation, and filtration. Dihalogenated N-DBPs typically peaked in the summer and early autumn with a relatively higher temperature, with the maximum levels of dichloroacetamide (DCAcAm), dichloroacetonitrile (DCAN), bromochloroacetonitrile, dibromoacetonitrile and dichloroacetone at 1.8, 6.3, 6.0, 2.6 and 1.8 μg L⁻¹ in the finished water, respectively. Also, the levels of all the dichlorinated N-DBPs were correlated with the ratio of dissolved organic nitrogen (DON) to dissolved organic carbon, implying autochthonous DON played an essential role in the formation of these DBPs. In contrast, the yields of trihalogenated DBPs [chloroform (CF), trichloronitromethane (TCNM) and trichloroacetone (TCAce)] appeared not to be significantly affected by seasons. CF and DCAN were the dominant species in trihalomethanes (THMs) and dihaloacetonitriles (DHANs), respectively. Bromine was more readily incorporated into DHANs to form brominated DBPs than THMs during pre-chloramination. Although pre-chloramination can ensure the finished water to meet with the current Chinese THM regulatory limits, the increased levels of TCNM and TCAce may be a new water quality concern.     

Formation of organochlorine compounds in kraft pulp bleaching processes

The most abundant volatile organochlorine compounds (VOCCs), trichloroacetic and dichloroacetic acids and AOX, were determined in bleaching effluent and waste water from three kraft pulp mills during ClO₂ bleaching. 0.6–7.7 g of VOCCs per ton bleached pulp were formed, the most abundant being chloroform and dichloroacetic acid methyl ester. Most of the VOCCs were removed during treatment, and it was estimated that 2–30 t of VOCCs would be removed annually from activated sludge treatment plants in Finnish kraft pulp mills using elemental chlorine free bleaching, most likely by volatilization. Dichloroacetic acid was formed in considerably higher amounts than trichloroacetic acid, and both compounds were removed effectively during treatment. The formation of all organochlorine compounds decreased considerably when non-chlorinated bleaching was employed.     

Formation of disinfection by-products in chlorinated swimming pool water.

The formation of five volatile disinfection by-products (DBPs: chloroform, bromodichloromethane, chloral hydrate, dichloroacetonitrile, and 1,1,1-trichloropropanone) by the chlorination of the materials of human origin (MHOs: hair, lotion, saliva, skin, and urine) in a swimming pool model system was examined. Chlorination reactions took place with a sufficient supply of chlorine residuals (0.84 mg Cl2/l < total chlorine < 6.0 mg Cl2/l) in 300 ml glass bottles containing either ground water or surface water as a reaction medium at 30 degrees C and pH 7.0, for either 24 or 72 h. A longer reaction period of 72 h or a higher content of organic materials led to the increased formation of DBPs. Of the DBPs formed by the reaction, chloroform was a major compound found in both ground and surface waters. The formation of chloroform and bromodichloromethane per unit total organic carbon (TOC) concentration was suppressed when all types of MHOs were added to the surface water that already contained DBP precursors such as humic substances. However, the formation of dichloroacetonitrile was promoted, probably due to the increased degradation reactions of nitrogen-containing compounds such as urea and proteins of human origin. In conclusion, the materials of swimmers' origin including hair, lotion, saliva, skin, and urine add to the levels of DBPs in swimming pool water, and any mitigation measures such as periodic change of water are needed to protect swimmers from elevated exposures to these compounds.     

Formation of volatile halogenated by-products during chlorination of isoproturon aqueous solutions

The present paper deals with the formation of volatile halogenated by-products (POX) during the chlorination (160 mg/l) of aqueous solutions of the herbicide isoproturon (40 mg/l). Chlorination reactions have been carried out over 48 h, at ambient temperature, at two pHs (6 and 9) and in the presence or not of bromide ions (80 mg/l). The main results obtained have been as follows: (1) in the presence of bromide, isoproturon degradation is rather fast and it results affected by pH, complete isoproturon degradation is achieved within 1 and 15 min at pH 6 and 9, respectively; (2) in the absence of bromide herbicide degradation is slow (complete degradation is achieved within 180 min) and it is not affected by pH; (3) at pH 6, regardless of the presence of bromide, the maximum amount of POX formed is low (approximately 15 micromol X-/l) and remains constant during the reaction; (4) at pH 9 the amount of POX formed is far greater and continuously increases during the reaction, reaching a value of about 110 micromol X-/l after 48 h; (5) two different groups of by-products have been identified by solid phase micro extraction (SPME)-gas chromatography (GC)-mass spectrometry (MS) for the reactions carried out with or without bromide; among them, aliphatic as well as aromatic by-products containing chlorine, bromine or both halogens are present even though the most abundant are halogenated-methane derivatives (haloforms); pH value affects the amount of these by-products but does not modify their chemical nature.     

Formation potentials of bromate and brominated disinfection by-products in bromide-containing water by ozonation

The ozonation involved in drinking water treatment raises issues of water quality security when the raw water contains bromide (Br^?). Br^? ions may be converted to bromate (BrO₃ ^?) during ozonation and some brominated disinfection by-products (Br-DBPs) in the following chlorination. In this study, the effects of ozone (O₃) dosage, contact time, pH, and Br^? and ammonia (NH₃-N) concentrations on the formation of BrO₃ ^? and Br-DBPs have been investigated. The results show that decreasing the initial Br^? concentration is an effective means of controlling the formation of BrO₃ ^?. When the concentration of Br^? was lower than 100 μg/L, by keeping the ratio of O₃ dosage to dissolved organic carbon (DOC) concentration at less than 1, BrO₃ ^? production was effectively suppressed. The concentration of BrO₃ ^? steadily increased with increasing O₃ dosage at high Br^? concentration (>900 μg/L). Additionally, a longer ozonation time increased the concentrations of BrO₃ ^? and total organic bromine (TOBr), while it had less impact on the formation potentials of brominated trihalomethanes (Br-THMFP) and haloacetic acids (Br-HAAFP). Higher pH value and the presence of ammonia may lead to an increase in the formation potential of BrO₃ ^? and Br-DBPs.     

Formation of oxidation by-products of the iodinated X-ray contrast medium iomeprol during ozonation

The present work describes the investigation of the formation of oxidation by-products of the iodinated X-ray contrast medium (ICM) iomeprol during ozonation in water treatment. Bench-scale investigations revealed that ICM can be partly oxidized during ozonation processes, whereas the ionic diatrizoic acid showed the lowest reactivity. Iomeprol, as a representative of ICM, was not fully mineralized during ozonation. Thus, unknown oxidation by-products were formed. Aqueous solutions of iomeprol were treated by ozonation in order to assess the formation of oxidation by-products. The by-products were characterized by different liquid chromatography methods including detection of single-stage mass spectra, product ion mass spectra, and induced in-source fragmentation for analysis of iodine containing oxidation by-products. Aldehyde and carbonyl containing compounds were proposed to be among the stable by-products. A derivatization step confirms that the aldehyde and carbonyl moieties are major functional groups in oxidation by-products of iomeprol. Furthermore, oxidation by-products of iomeprol were detected at the outlet of an ozone reactor at a full-scale waterworks. However, the toxicological relevance of the by-products is a major future research tasks.     

Polychlorinated dibenzothlophenes in bleached pulp mill effluents

Polychlorinated dibenzothiophenes, PCDBTs, have been analysed with HRGC/HRMS from different bleached pulp mill effluents. 2,3,7,8-TeCDBT was found to be the dominating TeCDBT isomer in some samples. The estimated concentrations of the TeCDBTs in the samples were < 1 to 60 pg/L. PeCDBTs and other higher chlorinated PCDBTs were not found (< 1 pg/L).     

饮用水消毒副产物研究状况

本文介绍了饮用水中消毒副产物的研究状况。其中重点介绍了饮用水的消毒方式及四类消毒副产物的产生、浓度、存在形态及影响因素等。简单介绍了饮用水中消毒副产物的采集、前处理方法及污染控制对策等     

Disinfection by-products in Finnish drinking waters

Disinfection by-products (DBPs) were measured in plant effluents of 35 Finnish waterworks, which utilized different treatment processes and raw water sources. DBPs were measured also from the distribution systems of three waterworks. Di- and trichloroacetic acids, and chloroform were the major DBPs found in treated water samples. The concentration of six haloacetic acids (HAA6) exceeded the concentrations of trihalomethanes (THMs). Chlorinated drinking waters (DWs) originating from surface waters contained the highest concentration of HAA6 and THMs: 108 and 26 microg/l, respectively. The lowest concentrations of DBPs were measured from ozonated and/or activated carbon filtrated and chloraminated DWs. Higher concentrations of HAA6, THMs, and adsorbable organic halogens were measured in summer compared to winter. The levels of chlorinated acetic acids, chloroform, and bromodichloromethane correlated positively with mutagenicity. Past mutagenicity levels of DWs were examined. A major reduction in the use of prechlorination, increased use of chloramine disinfection, and better removal of organic carbon were the most important reasons for the 69% decrease in mutagenicity from 1985 to 1994.     

Formation of hazardous by-products resulting from the irradiation of natural organic matter: comparison between UV and VUV irradiation

The use of ultraviolet (UV) or vacuum ultraviolet (VUV) photo-oxidation followed by biological treatment for the removal of natural organic matter (NOM) in drinking water is a potential water treatment technique under investigation. This paper reports on the trihalomethane formation potential (THMFP), the haloacetic acid formation potential (HAAFP), and formation of nitrite and peroxide following both UV and VUV irradiation of NOM prior to biological treatment. The total THMFP was found to decrease with increasing UV and VUV irradiation dose, although there was a linear increase in bromoform formation. Determination of the THMFP of NOM fractions obtained after irradiation, showed that the hydrophobic fraction was dominated by chlorinated species which accounted for the majority of the total THMFP, while bromoform was observed only in the hydrophilic fraction of NOM. VUV irradiation reduced the HAAFP with increasing dose, in contrast, UV irradiation had a limited effect on the overall HAAFP. Following UV or VUV irradiation, the chlorinated species accounted for the majority of HAAFP; however, significant formation of brominated haloacetic acid (HAA) was observed. The nitrate concentration of the untreated water directly influenced the concentration of nitrite produced as a consequence of UV and VUV irradiation. Hydrogen peroxide formation was greater during VUV irradiation than during UV irradiation. Samples exposed to various doses of UV or VUV irradiation (up to 138 J cm(-2)) were deemed non-cytotoxic (African green monkey kidney cells) and non-mutagenic (Ames test).     

Concentration of organochlorine pesticides in wine corks

Wine corks were extracted and analyzed for 23 organochlorine pesticides, including alpha-, beta-, and gamma-hexachlorocyclohexanes (HCH), hexachlorobenzene, DDT, DDE and DDD, chlordane, endosulfan, dieldrin, aldrin, and endrin. This was done to investigate the occurrence, concentrations, composition profiles, and possible sources of organochlorine contamination. All groups of compounds were detected in every sample investigated, with the exception of aldrin and endrin. The total concentrations of organochlorine compounds in all samples ranged from 75-120 ng/g lipid, and for most compounds, the concentrations of organochlorines in cork were consistent with published data for other plant tissues. Differences in the relative abundances of the various classes of organochlorine pesticides were substantial and were probably due to differences in the pesticide usage practices of the various regions in which the cork producing trees were grown.     

Residues of organochlorine pesticides in Alabama soils

A survey was made of 36 Alabama agricultural soils to assess residues of formerly used organochlorine pesticides. Compounds determined comprised alpha- and gamma-hexachlorocyclohexane, heptachlor, heptachlor-exo-epoxide, trans- and cis-chlordane, trans-nonachlor, dieldrin, toxaphene, DDT and DDE. Concentrations varied by several orders of magnitude among farms and appeared to be log-normally distributed. Highest concentrations (ng g(-1) dry soil, arithmetic means) were found for toxaphene (285+/-390) and DDTs (p,p'-DDE, 22.7+/-21.4; p,p'-DDT, 24.6+/-30.5; o,p'-DDT, 4.00+/-5.86; p,p'-DDD, 2.40+/-2.41) which were once heavily used in the southern USA. Pesticide residues were not proportional to soil organic carbon content indicating that residue concentrations were a reflection of pesticide application history and dissipation rates rather than air-soil equilibrium. Mean ratios of DDT/DDE in six regions of the state ranged from 0.39 to 1.5, and compound ratios for chlordanes and toxaphene were different from those in the technical mixtures.     

Accumulation of organochlorine contaminants in double-crested cormorants

Cormorant eggs and lipid samples from juvenile Cormorants were analyzed for 14 organochlorine contaminants. Low concentrations (geometric mean < 0.05 microg/g) of hexachlorobenzene (HCB), lindane, oxy-chlordane, heptachlor epoxide, dieldrin, endrin, mirex, DDD and DDT in eggs primarily reflected the wintering-ground origin of organochlorine contaminants. Overall geometric mean concentrations of DDE and PCBs in Cormorant eggs were 3.90 and 2.22 microg/g egg respectively, and would not affect reproduction or eggshell thickness. Eggshells averaged 0.44 mm in thickness and no correlation (r2 = 0.17) with log-transformed DDE residues in Cormorant eggs was evident. Only DDE and PCBs were detected in lipid samples from 5- to 8-week-old Cormorants (geometric mean approximately 1.0 microg/g lipid for each compound). The PCB: DDE ratios in Cormorant lipid from some individual colonies were 2-3.5 times greater than the ratio in eggs from the same colony, suggesting an accumulation of PCBs related to local diet. Juvenile Cormorants might serve as regional indicators of chemical residue contamination in Alberta, and provide a temporal perspective on changes in contaminant burdens in aquatic ecosystems.     

Chiral organochlorine pesticides in the atmosphere

We measured the enantiomeric fractions (EF) of various organochlorine pesticides in air samples from Indiana, Arkansas, and Louisiana collected in 2002–2003. Enantiomeric fractions for o,p′-DDD are reported here for the first time, and they suggest preferential depletion of one enantiomer over the other, with a mean value of 0.44. For the chlordanes, the EFs followed the same trends as reported in previous studies. EF values for trans-chlordane (TC) were slightly below 0.5, and values for cis-chlordane (CC) were slightly above 0.5. For cis-heptachlor epoxide (HEPX), the EF values averaged 0.65, indicating a clear preferential depletion of the (−)-enantiomer. For TC and CC, no clear distinction could be made between the values measured among the three sites, suggesting that it is not possible to use these EF values as “source signatures”. For HEPX, the Indiana site had significantly higher EF values than did the Arkansas site; this difference may reflect differences in the historic use of heptachlor in these two regions.     

Rainy River water quality in the vicinity of bleached kraft mills

Water and suspended solids samples were collected at four river stations and from two pulp and paper mill final effluents and analysed for a variety of organic contaminants. Juvenile fish were collected upstream and downstream of the mill discharges. Results showed significant mill inputs of PCBs, PAHs, chlorophenols, dioxins and furans which impacted downstream stations. Juvenile fish analysed downstream of the effluents indicated uptake of PCBs and chlorinated phenols.     

Residues of organochlorine pesticides in fishes in Sudan

Abstract

Cotton‐producing areas of the Centrol Sudan, bordered by the Blue and the White Nile, have been subjected to repeated applications of pesticides. This region is irrigated by a series of canals, the Gezira canals, which hold large amounts of fresh water. Lake Nubia at the Sudan‐Egypt border is another important fresh water reservoir and fisheries ground. Fish from both the Gezira and Lake Nubia showed elevated concentrations of pesticides, suggesting that continued pesticides application would endanger the equatic fauna of this region and the proposed fresh water fishery.     

Spectroscopic behavior of oxygenated combustion by-products

The oxygenated species, massively produced in the energy production plants based on combustion processes, constitute one of the most numerous categories of hazardous air pollutants. Therefore, development of real time diagnostic tools are needed in order to study their formation during combustion processes and to reveal their presence both in the exhaust and in the atmosphere. In this work, oxygenated compounds were identified inside fuel-rich premixed ethylene/air flames by means of ultraviolet fluorescence spectroscopy with the support of qualitative chemical analysis of the sampled combustion gases.

Strong band progression, typical of aldehydic functionality, were recognized in fluorescence spectra (λ_exc=355 nm) measured in the early oxidation region of premixed flames varying the equivalence ratio from 3.0 up 21.6. Downstream of the oxidation region, spectroscopic signatures of pyrolytic species were found to prevail on those peculiar of oxygenated compound. The position and the extension of the two main flame zones were found to depend on the flame conditions (C/O ratio) due to the effect of the C/O ratio on the temperature history along the flame axis. This correlation was interpreted on the basis of the measured axial temperature profiles.     

Evidence of natural organochlorine formation in peat bogs

Peat samples from four ombrotrophic and two minerotrophic peat bogs in New Brunswick, Canada, have been analyzed for polychlorinated dioxins and furans (PCDD/DF's) as well as other organochlorine compounds. Data from each bog show occasional low levels of 2,3,7,8-substituted tetra-through octachloro dioxins and furans. Mono-through trichlorodioxins and furans have also been identified.

A consistent pattern was observed among the TCDD's and TCDF's which was reproducible across all peat samples analyzed. A single TCDF isomer (2468-TCDF) predominates over all other isomers whereas two isomers of TCDD were prominent (1,3,6,8-TCDD and 1,3,7,9-TCDD). This distinct isomer pattern is present at all depths and is different from that of atmospheric deposition or known sources of PCDD/DF's (eg. fly ash, pulp and paper effluent etc). The pattern is replicated with in vitro oxidative coupling of 2,4-dichlorophenol at pH 2.9 using a commercially available chloroperoxidase from the fungus Caldariomyces fumago.

Significant incorporation of ³⁶Cl-occurred in peat. Autoclaving decreased incorporation while adding casein hydrolysate increased it. The incorporation mirrored the metabolic activity (CO₂ production) of samples consistent with organochlorine synthesis being due to biological activity.

Total Organic Halide (TOX) levels in peat show a wide range in values reaching ca. 1000 ppm at mid-depth in the ombrotrophic Kelly's Bog. TOX in Kelly's Bog occurs at all depths and, since the topography probably excludes leaching from surrounding areas, a local origin of organochlorines is suggested.

Chloroform and a range of chlorinated aromatic compounds (chlorophenols, chlorophenoxy and chlorobenzoic acid derivatives) have also been identified in peat.

Our findings to date are consistent with hypothesis for a biogenic origin for at least some of the organochlorine compounds, including some of the PCDD/DF's, found in peat bogs.     

Trends of organochlorine compounds in Finnish inland waters

Caged common lake mussels (Anodonta piscinalis) have been used in the monitoring of organochlorine compounds in pulp and paper mill recipient watercourses of Finland annually from 1984 to 1998. Statistically significant decreasing trends of chlorophenols and chloroguaiacols originating from chlorobleaching were observed in all recipients in parallel with the decreasing discharges from the mills. Metabolites of chlorophenols, chloroanisoles and chloroveratroles had no or slightly increasing trends. Elevated PCB concentrations were measured in four watercourses. In two areas, PCBs were found to be significantly increasing, in two other cases they showed no trend. A mill producing recycled paper was apparently responsible for an increase of PCBs and DDE in recipient watercourses. Overall decreases were observed for other chlorohydrocarbons except for DDT. Material flows of chlorohydrocarbons were positively correlated with waterflows (Q) in some cases.