Long term changes in polychlorodibenzo-p-dioxin concentrations in wood treated with technical pentachlorophenol

Wood samples treated with technical pentachlorophenol (PCP), technical sodium pentachlorophenoxide (NaPCP) and octachlorodibenzo-p-dioxin have been exposed outdoors for periods up to $\text{2}\text{1}\text{2}$ years. Analysis of extracts from the samples show that photolytic reductive dechlorination of highly chlorinated dibenzo-p-dioxins to less chlorinated isomers occurs. However there is no discernible increase in polychlorodibenzo-p-dioxin concentrations in the technical PCP treated wood presumably because further photolytic reactions and volatilisation compete effectively with the photolytic formation. There is no evidence for formation of octachlorodibenzo-p-dioxin (OCDD) in technical PCP treated wood in this study, probably because photolytic destruction and volatilisation compete effectively with formation reactions when the initial OCDD concentration is relatively high.     

Bioaccumulation of pentachlorophenol by killifish (Fundulussimilus)

Killifish ($\text{Fundulus}$$\text{similis}$) were exposed in the laboratory to pentachlorophenol (PCP) at concentrations of 57 to 610 μg PCP/L. Bioaccumulation reached a plateau value of about 53 by 168 hrs and remained at this level for at least 72 hrs. One-half the plateau value was reached in about 25 hrs. Following exposure, fish placed in PCP-free aquaria lost PCP rather slowly ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{～ 4.7}\text{days}$). The depuration data were suggestive of a pool of PCP which was lost more rapidly ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{～ 4.2}\text{hrs}$). The results of this study are compared to similar studies in other species. The bioaccumulation factors measured in this study agree relatively well with those in other marine species, but are lower than reported for fresh water species. Possible reasons for this difference are discussed.     

Treated wood in livestock facilities: relationships among residues of pentachlorophenol, dioxins, and furans in wood and beef.

Wood and other environmental samples were collected from sites that produced beef with higher than average residues of dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF). Analyses of these samples for PCDD/Fs and pentachlorophenol (PCP) indicated that the high beef residues were associated with PCP-treated wood in the animal facilities. Concentrations of PCDD/Fs in wood as toxic equivalents ranged from 10 to 320,000 pg/g. These concentrations were closely related to the concentrations of PCP, indicating that analysis for PCP provides an economical method to identify wood with high concentrations of PCDD/Fs. Further evidence for the PCP-treated wood as the source of the beef residues is provided by the similarity of the congener profiles in beef from the sites and those profiles predicted from the profiles in wood.     

Field-scale leaching of arsenic, chromium and copper from weathered treated wood

Earlier studies documented the loss of wood preservatives from new wood. The objective of this study was to evaluate losses from weathered treated wood under field conditions by collecting rainfall leachate from 5 different wood types, all with a surface area of 0.21 m². Wood samples included weathered chromate copper arsenate (CCA) treated wood at low (2.7 kg/m³), medium (4.8 kg/m³) and high (35.4 kg/m³) retention levels, new alkaline copper quat (ACQ) treated wood (1.1 kg/m³ as CuO) and new untreated wood. Arsenic was found to leach at a higher rate (100 mg in 1 year for low retention) than chromium and copper (<40 mg) in all CCA-treated wood samples. Copper leached at the highest rate from the ACQ sample (670 mg). Overall results suggest that metals' leaching is a continuous process driven by rainfall, and that the mechanism of release from the wood matrix changes as wood weathers.     

Residential and biological exposure assessment of chemicals from a wood treatment plant

This paper evaluates the results of contamination of residents and residential homes located in close proximity to a Wood Treatment Plant. The plant has produced treated wood products continuously since 1904. The principle chemicals used to treat the wood, which is primarily used for railroad ties (oblong objects laid perpendicular to the rails to act as a base for the tracks), are creosote and pentachlorophenol. For a number of years, the plant burned treated waste wood products containing creosote and pentachlorophenol. First the plant pressure impregnates the wood with creosote and pentachlorophenol, and then the wood is stacked on open ground to allow it to air dry. Chemicals from recently treated wood ties are allowed to evaporate into the air or drip onto the ground surrounding the stacked wood. Small drainage ditches carry the liquid wastes into larger water channels where eventually the waste streams are discharged into a river adjacent to the plant. The river serves as a source of drinking water for the nearby community. Prevailing wind patterns favor a drift of air emissions from the plant's boiler stack over the nearby community and its residents. Over the past few years, the town's residents have become increasingly concerned about their health status and have voiced concerns regarding multiple health problems (including cancer), possibly associated with plant discharges. The intention of this study is to examine a representative sample of the potentially affected residents and to evaluate their residential environment for the presence of dioxin and/or its congeners. Data obtained from EPA's Toxic Release Information (TRI) database revealed the plant routinely discharged creosote, pentachlorophenol, dioxin and dioxin-like compounds into the ambient air via fugitive air emissions and surface waste waters. Sampling of household dust and water sediment within and outside of residences within a 2-mile radius of the plant revealed the presence of significantly elevated levels of dioxins, principally octachlorodibenzo-p-dioxin (OCDD) and 1,2,3,4,6,7,8-hepta-CDD. Biomonitoring of 29 subjects identified the presence of significantly elevated chlorinated dioxins and furan levels (OCDD=1049 ppt for exposed and 374 ppt for controls and 1,2,3,4,6,7,8-hepta CDD=132 ppt for exposed and 45.1 ppt for controls). These levels are consistent with exposures to pentachlorophenol in this group of subjects. And they confirm the presence of unsafe levels of chlorinated dioxins in these persons.     

Chlordane compounds residues in Weddell seals (Leptonychotesweddelli) from the Antarctic

Weddell seal samples taken from the Antarctic have been found to be contaminated with chlordane compounds. ΣChlordane ($\text{cis}\text{-chlordane}\text{+}\text{cis}\text{-nonachlor}\text{+}\text{trans}\text{-nonachlor}\text{+}\text{oxychlordane}$) was present in blubber of seals at the range of 12 - 62 ng/g fresh weight. The order of chlordane compound concentrations was $\text{trans}\text{-nonachlor}\text{>}\text{oxychlordane}\text{>}\text{cis}\text{-nonachlor}\text{>}\text{cis}\text{-chlordane}$. Relative aboundance of $\text{cis}$-chlordane in Σchlordane is higher than that in humans. A probable explanation for their occurrence in the Antarctic is an airborne transport.     

Removal of alpha-pinene from gases using biofilters containing fungi

Biofiltration is cost-effective for the treatment of gases containing low concentrations of volatile organic compounds $\text{(<3}\text{g}\text{m}{}^{\mathrm{-3}}\text{)}$. However, conventional biofilters, based on compost and bacterial activity, face problems with the elimination of hydrophobic compounds. Besides that, biofilter operational stability is often hampered by acidification and drying out of the filter bed. To overcome these problems, biofilters with fungi on inert packing material have been developed. Fungi are more resistant to acid and dry conditions than bacteria, and it is hypothesised that the aerial mycelia of fungi, which are in direct contact with the gas, can take up hydrophobic compounds faster than flat aqueous bacterial biofilm surfaces. Alpha-pinene was chosen as a model compound. It is an odorous compound emitted by the wood processing industry. In $\text{2}\text{l}$ biofilter columns four different packing materials were tested: perlite, expanded clay granules, polyurethane foam cubes and compost. The filters were inoculated with forest soil and ventilated with gas containing alpha-pinene. Start up took 1–2 months and removal efficiencies of more than 90% were observed, but mostly ranged from 50% to 90% due to overloading. In the filters containing perlite, clay, polyurethane and compost volumetric removal capacities of, respectively, 24, 33, 38 and $\text{24}\text{g}$ alpha-$\text{pinene}\text{m}{}^{\mathrm{-3}}$ filter $\text{bed}\text{h}{}^{\mathrm{-1}}$ were attained and the gas pressure drops in the $\text{60}\text{cm}$ high filter beds measured at a superficial gas velocity of $\text{35}\text{m}\text{h}{}^{\mathrm{-1}}$ were 70, 550, 180 and $\text{250}\text{Pa}$. The results indicate that it is possible to develop biofilters based on the action of fungi with higher elimination capacities for alpha-pinene as reported in literature for bacterial biofilters. The use of polyurethane foam cubes is preferred because of the low gas pressure drop in combination with a high volumetric elimination capacity.     

The effect of cadmium ion on the growth,photosynthesis, and nitrogenase activity of Anabaenainaequalis

The growth of $\text{Anabaena}$$\text{inaequalis}$ was significantly inhibited by Cd²⁺ concentrations greater than 0.02 ppm (μg/ml) and completely inhibited at 0.06 ppm (Day 12). Cadmium had no significant effect upon the lag phase of growth or the culture doubling time, but caused the retardation phase to arrive sooner. One ppm Cd²⁺ significantly inhibited the rates of both photosynthesis and acetylene reduction, by $\text{A}$. $\text{inaequalis}$, with complete inhibition at 4 and 20 ppm respectively. Cell sensitivity increased directly with exposure time. Cadmium caused some cell lysis of $\text{A}$. $\text{inaequalis}$ and induced an increase in filament length, heterocyst frequency, and a loss of cellular contents from filament apical cells. The cellular abnormalities observed and the fact that toxicity increased with longer exposure times, suggested that metal toxicity resulted from effects of Cd²⁺ taken up by cells rather than Cd²⁺ at the cell surface.     

EPA SITE Demonstration of the BioTrol Soil Washing Process

A pilot-scale soil washing process, patented by BioTrol, Inc., was demonstrated on soil contaminated by wood treating waste, primarily pentachlorophenol (PCP) and creosote-derived polynuclear aromatic hydrocarbons (PAHs). Although soil washing was the main object of this demonstration, the treatment train that was evaluated included two other BioTrol technologies for treatment of waste streams from the soil washer. The three technologies were: ? The BioTrol Soil Washer (BSW)—a volume reduction process, which uses water to separate contaminated soil fractions from the bulk of the soil.

? The BioTrol Aqueous Treatment System (BATS)—a biological water treatment process.

? The Slurry Bioreactor (SBR)—a BioTrol biological slurry treatment process conducted in an EIMCO BIOLIFT^tm reactor.

The sandy soil at the site, consisting of less than 10 percent of fines, was well suited for treatment by soil washing. The soil washer was evaluated in two tests on soil samples containing 130 ppm and 680 ppm of PCP, respectively.

The BSW successfully separated the feed soil (dry weight basis) into 83 percent of washed soil, 10 percent of woody residues, and 7 percent of fines. The washed soil retained about 10 percent of the feed soil contamination while 90 percent of the feed soil contamination was contained within the woody residues, fines, and process water.

The soil washer achieved up to 89 percent removal of PCP and 88 percent of total PAHs, based on the difference between their levels in the as-is (wet) feed soil and the washed soil. PCP concentrations of 14 ppm and 87ppm in the washed soil were achieved from PCP concentrations of 130 ppm and 680ppm in the feed soil. Concentrations of total PAHs were reduced from 247 ppm to 42 ppm and 404 ppm to 48 ppm, respectively, in the two tests.

The BATS degraded up to 94 percent of PCP in the process water from soil washing. PAH removal could not be determined due to low influent concentrations.

The SBR achieved over 90 percent removals of PCP and 70 to 90 percent removals of PAHs from the slurry of contaminated fines from soil washing. However, steady state operation was not achieved during the single test and the results were variable.

Cost of a commercial-scale soil washing, assuming use of all three technologies, was estimated to be $168 per ton of soil treated. Incineration of woody material accounts for 76 percent of the cost.     

Substitutes for phosphate containing washing products: Their toxicity and biodegradability in the aquatic environment

The toxicity of nitrolotriacetic acid (NTA), citrex-S-5, sodium alluminium silicate (NAS), carboxymethyloxysuccinate (CMOS), linear alkylbenzene sulfonate (LAS) and soap was examined using bacteria ($\text{Pseudomonas}$$\text{fluorescens}$), algae ($\text{Chlorella}$$\text{vulgaris}$ and $\text{Microcystis}$$\text{aeruginosa}$), crustaceans ($\text{Daphnia}$$\text{magna}$), insects ($\text{Aedes}$$\text{aegypti}$), fishes ($\text{Poecilia}$$\text{reticulata}$ and $\text{Oryzias}$$\text{latipes}$) and amphibians ($\text{Xenopus}$$\text{laevis}$). The biodegradability of NTA, citrex-S-5, CMOS and LAS was studied in the OECD-test.The acute toxicity of the compounds differed largely with the organisms tested (up to a factor 1,000). Based on the results of the short-term toxicity tests (with all test organisms) and the long-term toxicity tests (with $\text{Daphnia}$$\text{magna}$ and in case of LAS also with $\text{Poecilia}$$\text{reticulata}$) the following no-observed-effect concentrations (NOEC) could be derived: LAS 3.2 mg/1; NAS and soap 10 mg/1; CMOS 32 mg/1; NTA 100 mg/1 and citrex-S-5 320 mg/1. However, testing different samples of one test compound may result in marked differences in toxicity (e.g. NAS: a factor 32).All compounds tested showed to be biodegradable as the percentage DOC decreased more than 80% within four weeks. CMOS biodegraded quickly, whereas citrex-S-5 and LAS showed a somewhat slower rate of degradation. In contrast to the other compounds NTA required an adaptation period of 1 week.     

Fate of 3,3′,4,4′-tetrachloroazobenzene in soybean plants grown in treated soils

Three soils of varying organic matter (OM) concentrations (0, 1.7 and 57%) were treated with 3,3′4,4′-tetrachlorazobenzene (TCAB) at the 25 ppm level. Germinated soybeans$\text{(Glycine}$$\text{max}$ (L.) Merr.) were planted in the treated soils, along with controls, and grown for 12 days. The shoots, roots and soil were air-dried and analyzed for TCAB and 3,3′,4,4′-tetrachloroazoxybenzene (TCAOB). TCAB appears to translocate from the treated soil into the plant shoots and roots. Residue levels varied with the percentage organic matter of each soil; levels as high as 58.4 ppm were identified in roots of soybeans grown in 1.7% OM soil and 0.620 ppm in the shoots from 0% OM soil. TCAOB was identified in soil and root extracts with the highest levels in soybean roots grown in 0% OM soil, 0.317 ppm. Residues of TCAB and TCAOB decreased in soil and root and shoot tissues as percentage OM increased. Bound residues of TCAB were released from roots grown in 0% OM soil by refluxing with boron trifluoride methanol (BF₃CH₃OH).     

Phthalates and the aquatic environment: Part I The effect of di-2-ethylhexyl phthalate (DEHP) and di-isodecyl phthalate (DIDP) on the reproduction of Daphnia magna and observations on their bioconcentration

$\text{Daphnia magna}$ were exposed to di-2-ethylhexyl phthalate (DEHP) and to di-isodecyl phthalate (DIDP) at nominal concentrations up to 100 μg/1 over a 21 day period. The phthalates had no effect on reproduction, and the parent $\text{Daphnia}$ showed bioconcentration factors of 209 (DEHP) and 116 (DIDP) as determined by ¹⁴C analysis.     

Organochlorine residues in roof timbers and possible implications for bats

In Britain, many species of bat regularly use buildings as roosts. DDT, DDE, dieldrin (HEOD) and gamma-HCH (lindane) have been detected in carcasses of bats that had died a short while before they were found. Roof timbers may be a source of this contamination. This study reports concentrations of organochlorines in (i) roof timbers known to have been treated in the past (spot samples; n - 17) and (ii) timbers before and after treatment with commercial permethrin formulations (pre-treatment and post-treatment samples, n = 11). Gamma-HCH was detected in 13 spot samples and HEOD in 6. Where present, mean (+/-1 SE) concentrations in wood were 15.6+/-6.5 microg g-1 WW (n = 13) and 25.0+/-11.8 microg g-1 WW (n = 6), respectively. DDT was not detected in any spot samples, but permethrin was detected in four (1264+/-567 microg g(-1) WW) samples, but not in the corresponding pre-treatment samples; in one other pair of samples, concentrations of gamma-HCH increased from 74 to 2468 microg g-1 WW after treatment. Both DDT and HEOD occurred in low (<2 microg g-1 WW) concentrations in five post-treatment samples and in one and zero pre-treatment samples, respectively; the highest dieldrin concentration measured was 30.9 microg g-1 WW. Permethrin was not detectable in any pre-treatment samples but was present in ten post-treatment samples in concentrations ranging from 93 to 2995 microg g-1 WW. The spot results suggest that low concentrations of organochlorines can persist in treated roof timbers for at least 13 years post-treatment. Occasionally, these pesticide residues in timber may be of sufficient magnitude to result in bats absorbing a substantial proportion of a lethal dose. Results also suggest that there is organochlorine contamination of permethrin formulations and that the solvents used in new applications of pesticide may re-mobilise organochlorines already present in wood.     

A baseline study on the concentrations of chlordane-, PCB-and DDT-compounds in Finnish fish samples in the year 1982

113 Fishes (pike, vendace and roach) samples were analyzed for chlordane, PCB-and DDT-compounds. The average concentrations in pike ($\text{Esox lucius}$) muscle tissue in Finnish lakes were 0.05, 0.01 and 0.01 mg/kg wet weight for PCB compounds, total DDT and chlordanes respectively. The results show that chlordanes are evenly distributed in the Finnish environment which indicate that the main part of chlordanes in Finnish fish is due to long range transportation.     

The fate of dichlorvos in soil

Experiments were conducted to determine the factors responsible for the loss (adsorption, chemical hydrolysis, microbial degradation, etc.) of dichlorvos (2,2-dichlorovingl $\text{0}$,$\text{0}$-dimethyl phosphate) in soil perfusion systems of Houston Black clay. The rate of disappearance from the perfusate (hence the rate of dichlorvos degradation in soil) was related directly to the presence of $\text{Bacillus}$$\text{cereus}$ in the perfusion system, the pH of the system, and the extent of dichlorvos adsorption. Gas liquid chromatographic analyses of the perfusates showed that dichlorvos disappearance was rapid when $\text{B}$. $\text{cereus}$ was added to a previously sterilized soil perfusion system (50% in 3.9 days). Under sterile conditions, 50% of the added dichlorvos was recovered after 10 days. When $\text{B}$. $\text{cereus}$ was added to a mineral salts medium containing dichlorvos as sole ccrbon source, 49% of the initial dichlorvos concentration was degraded in 4 days. The organism was not capable of utilizing dichlorvos as a sole phosphorus source. Chemical hydrolysis of dichlorvos in aqueous, buffered, soil-free systems showed that hydrolysis did not occur in very acid systems (<pH 3.3), but increased with increasing pH values (26% in 4 days at pH 6.9), and was rapid at pH 9.3 (> 99% in 2 days). The extent of dichlorvos adsorption was determined by comparing the initial loss of dichlorvos in a sterile, soil-free extract solution with the initial loss in a sterile soil perfusion system. The rapid initial disappearance of dichlorvos in the presence of sterilized soil was attributed to soil adsorption of the pesticide. After 10 days both systems contained equal concentrations (50%) of dichlorvos. Non-biological mechanisms accounted for 70% of the total degradation of dichlorvos, while bacterial degradation accounted for 30% in the soil perfusion systems.     

Sources of PCDD/Fs, non-ortho PCBs and PAHs in sediments of high and low impacted transboundary rivers (Belgium-France)

PAHs, PCDD/Fs and non-ortho PCBs have been assessed in Yser and Upper-Scheldt river sediments. Higher contamination levels were observed in the Upper-Scheldt sediments: maximum concentrations for the 16 US-EPA PAHs, PCDD/Fs and non-ortho PCBs respectively amount to 8.9 mg kg⁻¹, 12 ng TEQ kg⁻¹ and 5.1 ng TEQ kg⁻¹. Diagnostic PAH ratios in sediments and atmospheric samples suggest that the PAH compounds are from pyrolytic origin, more specifically combustion processes. The huge consumption of coal in cokes-ovens and smelters and its use for house-heating in Northern France, although decreasing during the last decades, are in support of that suggestion. PCDD/F fingerprints in sediments and deposition material indicate that OCDD is the dominant congener. In addition use of pentachlorophenol (PCP) in the past led to a minor contribution of PCDD/Fs in our sediment samples. Non-ortho PCBs form a substantial fraction of the total TEQ concentrations observed in the sediments. Since the 1980s and 1990s a substantial reduction of the PCDD/F sediment concentrations is observed, but this is not the case for the PAHs.     

Effect of long term exposure to petroleum on mixed function oxygenases in fish: Further support for use of the enzyme system in biological monitoring

A number of long term, low level petroleum hydrocarbon exposures were carried out from 1978 to 1981 in order to further evaluate use of the mixed function oxygenase (MFO) system in biological monitoring. The studies involved exposure, at ambient temperatures, of fish from three separate families including (a) spawning codfish ($\text{Gadus morhua}$), (b) post-spawned sculpins ($\text{Myoxocephalus octodecemspinosus}$), and (c) gonadally maturing flounder ($\text{Pseudopleuronectes americanus}$). MFO activity remained elevated approximately four-fold in the liver, and three-fold in the gills of codfish exposed for four months to water concentrations of 0.30–0.60 ppm petroleum, at ?1-1°C. Similarly, liver enzyme activity remained elevated approximately three-fold in sculpins exposed to very low levels (0.15–0.20 ppm) of petroleum for three months, at 4–12°C. Results indicate that several years may be required before hydrocarbon concentrations are reduced in petroleum contaminated sediments, such as those heavily impacted by oil spills, to non-inducing threshold levels. Oil contaminated sediment was, even after a year of weathering, quite effective in inducing a high level of MFO activity (seven-fold) in flounder, at 11-6°C. A number of factors that might detract from use of the mixed function oxygenase system in biological monitoring were not realized in these long term studies with petroleum hydrocarbons.     

Soluble carbohydrates in bean leaves transformed into oxidant-tolerant tissues by EDU treatment

Improved gas-liquid chromatography techniques were used to evaluate the effects of EDUa on soluble leaf carbohydrates in $\text{Phaseolus vulgaris}$ L. ‘Bush Blue Lake 290’. This snap bean cultivar is normally rather sensitive to 0₃ but becomes highly tolerant when treated systemically with EDU. Less than 24 h is required to induce the resistance. Standardized trifoliate leaves from EDU-treated and control plants were sampled 48 h after treatment. Additional plants were sampled 48 h after treatment. Additional plants were exposed to 0₃ one day after EDU soil application to assess the plant tolerance induced. The optimal dose required to enhance oxidant tolerance was 50 mg/pot.Major sugars in both EDU-treated (0₃-tolerant) and untreated (0₃-sensitive) leaves were glyceraldehyde, erythritol, fructose, glucose and sucrose. $\text{Myo}$-inositol, ribose and arbitol were present in lesser or trace amounts. EDU-treatment resulted in significant increases (35–62%) in all soluble carbohydrates except glyceraldehyde and $\text{myo}$-inositol. Implications relating to plant tolerance, to oxidants and stress-induced senescence are discussed.