Modular containers for microcosm and process model studies on the fate and effects of aquatic contaminants

Container modules are described for the laboratory simulation of selected processes and ecosystems that are representative of lentic environments. Emphasis is placed on design features permitting mass balance accountability of contaminant residues and procedural cautions required for the proper use of the described systems in environmental simulations. Experiments on the efficiency of container modules for microbial mineralization studies were conducted using ¹⁴CNaHCO₃, and acidification resulted in a ¹⁴CCO₂ recovery of $\text{97.3 ± 4.7\% (}\text{x}\text{?}\text{± SD}\text{)}$. The trapping efficiency of pesticides volatilized from water and glass surfaces was investigated using the same module and the mean recoveries of ¹⁴C-fonofos and ¹⁴C-trifluralin were 114.2 ± 3.2% and 95.2 ± 3.5%, respectively. The mass balance capabilities of the system was also demonstrated for extended microcosm exposures to ¹⁴C-trifluralin.     

Environmental photochemistry of PCDDs. Part I. Kinetics and quantum yields of the photodegration of 1,2,3,4,7-penta- and 1,2,3,4,7,8-hexachlorodibenzo-p-dixin in aqueous acetontrile

For the determination of the quantum yields of 1,2,3,4,7-pentachlorodibenzo-$\text{p}$-dioxin ($\text{1}$) and 1,2,3,4,7,8-hexachlorodibenzo-$\text{p}$-dioxin ($\text{2}$), ten Pyrex glass photochemical cells were constructed and their correction factors determined. Quantum yields at 313 nm for $\text{1}$ and $\text{2}$ in aqueous acetonitrile (4:6 v/v) were (9.781 ± 2.376) 10^?5 and (1.096 ± 0.020) × 10^?4, respectively. These quantum yields and the measured absorption spectra were used to estimate the environmental phototransformation first-order rate constants and photochemical half-lives of $\text{1}$ and $\text{2}$ in water under conditions of variable sunlight intensity during various seasons from solar intensity data available in the literature. In summer, typical half-lives for the phototransformation of $\text{1}$ and $\text{2}$, respectively, near the surface of water bodies at 40° north latitude would be 364 ± 88 and 151 ± 3 h; whilst such values in winter would be 1257 ± 309 and 518 ± 10 h.     

Photochemistry and environment. VII- The photohydrolysis of chlorobenzene: Studies of the excited state involved

Chlorobenzene excited in dilute aqueous solution is transformed quantitatively into phenol ($\text{ф= 0.10±0.02}$). This reaction involves a triplet state, since it is quenched by biacetyl and sensitized by ketones. Based on quenching experiments, the lifetime of the lowest triplet of chlorobenzene was measured as 30 ns. From the sensitized phosphorescence of biactyl, the quantum yield of intersystem crossing (S₁→T₁) was found to be 0.6 ±0.1. The photophysical characteristics of chlorobenzene are identical in acetonitrile (). Photosensitization of the photohydrolysis is observed with acetone and acetone D6 in aqueous solution. The quantum yield of the sensitized photohydrolysis is limited to 0.06±0.01. Hexadeuterated acetone appeared to be a more specific photosensitizer than acetone.     

Environmental dynamics of phosphate esters. III. Comparison of the bioconcentration of four triaryl phosphates by fish

Uptake, clearance and extent of metabolism of ¹⁴C-labelled t-butylphenyldiphenyl phosphate (t-BPDP), tri-m-cresyl phosphate (mTCP), tri-p-cresyl phosphate (pTCP) and triphenyl phosphate (TPP) were studied in rainbow trout ($\text{Salmo}$$\text{gairdneri}$) and fathead minnows ($\text{Pimephales}$$\text{promelas}$) using short-term static exposures (50 and 5 μmg/L). Bioconcentration factors for pTCP, mTCP, TPP and tBPDP calculated by use of total radioactivity in whole fish were 1420, 784, 573 and 1096 respectively, for rainbow trout and 928, 596, 561 and 1010 respectively, for fathead minnows. Differences in rates of clearance and biotransformation among the four compounds were more closely related to their ease of hydrolysis than to hydrophobicity.     

Blood analysis of rabbits exposed to nitrogen monoxide

Rabbits exposed to NO-containing atmospheres develop an EPR signal in their blood which can be detected with good sensitivity following dithionite reduction and freezing to 160 K. The spectroscopic parameters indicate that NO is bound preferentially to the α chains of hemoglobin in the quaternary T state. The EPR signal intensity increases with time and with the concentration of NO but decreases rapidly ($\text{T}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{? 15}\text{min}$) when the rabbits are returned to clean air.     

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.     

Kinetics of oxidation of methylhydrazines in water. Factors controlling the formation of 1,1-dimethylnitrosamine

The kinetics of oxidation of methylhydrazine ($\text{MMH}$) and 1,1-dimethylhydrazine ($\text{UDMH}$) by dissolved oxygen in water has been measured at various acidities as a function of catalyst (cupric ion) concentration. In dilute solutions the oxidation occurs through a cupric ion catalyzed process as well as by an uncatalyzed step. The extent of formation of nitrosodimethylamine ($\text{NDMA}$) depends upon the initial $\text{UDMH}$ concentration. In dilute solutions $\text{NDMA}$ is not formed, but in more concentrated solutions, $\text{NDMA}$ formation increases with increasing $\text{UDMH}$ content, reaches a maximum at 60–80% $\text{UDMH}$ (by volume) and then decreases. The $\text{NDMA}$ yield appears to approximately parallel the viscosity of the medium, and it is speculated that the factors which control viscosity may also be responsible for governing $\text{NDMA}$ formation.     

Photochemistry of pesticides, 3: Photolysis of methyl 2-benzimidazolecarbamate (Carbendazim) in the presence of singlet oxygen

The photolysis of methyl 2-benzimidazolecarbamate (Carbendazim, $\text{1}$) in methanol and in the presence of singlet oxygen, was studied. Dimethyl oxalate $\text{4}$, 2-aminobenzimidazole $\text{7}$, benzimidazole $\text{9}$, N,N′-dicarbomethoxyguanidine $\text{13}$, monocarbomethoxyguanidine $\text{14}$, monocarbomethoxyurea $\text{15}$, and 2-guanidinobenzimidazole $\text{17}$, were isolated and identified in this reaction.A mechanism that accounts for the formation of the photoreaction products, is presented.     

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.     

Determination of vapor pressures for chloroguaiacols,chloroveratroles, and nonylphenol by gas chromatography

Vapor pressures of six chlorinated phenols were measured by capillary gas chromatography using a 1.0-m BP-1 bonded phase column. GC-determined vapor pressures (P_GC) were correlated with known liquid-phase vapor pressures (P_L) by the equation: Log P_GC = 1.026 Log P_L — 0.132, r² = 0.975 (vapor pressures in pascals). This relationship was used to estimate P_L for chloroguaiacols, chloroveratroles, and 4-nonylphenol from their experimental P_GC.     

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.     

Aqueous solubility of polychlorinated dibenzo-p-dioxins determined by high pressure liquid chromatography

Water solubilities (S_W) determined by the HPLC generator column method are reported for a series of chlorinated dibenzo-$\text{p}$-dioxins (PCDDs) with S_W ranging from 0.4 ng/L (ppt) for octa-chlorodibenzo-$\text{p}$-dioxin to 430 ng/L for 1,2,3,7-tetrachlorodibenzo-$\text{p}$-dioxin at 20°C. A correlation is demonstrated between S_W and HPLC capacity factors (k′) for these extremely hydrophobic compounds, allowing calculation of S_W of PCDDs from k′ and melting point data.     

Toxicite aigue du vanadium vis-a-vis de quelques especes benthiques et phytoplanctoniques marines

$\text{Acute toxicity of vanadium to some marine benthic and phytoplanktonic species}$The acute toxicity of vanadium as sodium metavanadate to three benthic ($\text{Carcinus}$$\text{maenas}$, $\text{Mytilus}$$\text{galloprovincialis}$, and $\text{Nereis}$$\text{diversicolor}$) and three phytoplankton species ($\text{Dunaliella}$$\text{marina}$, $\text{Prorocentrum}$$\text{micans}$ and $\text{Asterionella}$$\text{japonica}$) were studied. In general the phytoplankton were found to be more sensitive than the benthic organisms used in our experiments. Considering the results from LC₅₀ (9 days) experiments, the organisms, can be classified in the following decreasing order of sensitivity: $\text{D}$. $\text{marina}$ (0.5 ppm), $\text{A}$. $\text{japonica}$ (2 ppm), $\text{P}$. $\text{micans}$ (3 ppm), $\text{N}$. $\text{diversicolor}$ (10 ppm), $\text{C}$. $\text{maenas}$ (35 ppm), $\text{M}$. $\text{galloprovincialis}$ (65 ppm).     

Decomposition of benzo (a) pyrene deposited on glass fiber filters and exposed to sunlight

Measurements of Benzo (a) Pyrene deposited on glass fiber filters exposed to solar radiation indicate a time dependent exponential decrease. Possible impl$\text{i}$ cations of this phenomenon in the measurements of B(a)P in particulate samples are discussed.     

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.     

Selectivity of Euphorbia lathyris L., to chlortoluron results from the accumulation of the herbicide in the leaves

$\text{Euphorbia lathyris L.}$, was treated for 24 h. with 0.1, 1 and 10 ppm chlortoluron. The induction kinetic of the fluorescence on the whole leaf was registered during the following 15 days. A recovery of $\text{E. lathyris}$ seedlings and an accumulation of chlortoluron in leaves was observed. The fluorescence levels obtained on the leaves emerged after the treatments were similar to the one observed on the control plants. This explains the detoxification mechanism as an accumulation of chlortoluron in the leaves present during the treatment.     

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.     

Uptake,depuration and biotransformation of anthracene by the scud Pontoporeia hoyi

Uptake, depuration and biotransformation rates of ¹⁴C-anthracene were determined for Pontoporeia hoyi, the dominant benthic invertebrate in the Great Lakes, at 4°, 7°, 10° and 15°C. The uptake rate constants for anthracene increased from 136±22 h^?1 (n=4, $\text{X}\text{?}\text{±1}\text{SD}$) to 215±45 h^?1 (n=4) over the temperature range studied and were seasonally dependent. The depuration rate constant at the apparent optimum temperature of 7°C was 0.015 h^?1 for anthracene. The biotransformation ability of P. hoyi is low, and degradation of anthracene was undetectable even after exposures of 48 h. The bioconcentration factor can be predicted from the uptake and depuration kinetics to be approximately 16,800 at 4°C. These experiments imply that P. hoyi may be very important in food chain biomagnification of some toxic organics.     

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.